- Asymmetric hydroformylation of vinyl acetate with BINAP-rhodium(I) complexes
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Complexes of (R)-BINAP (BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) derived from the available rhodium precursors Rh(acac)(CO)2 and [Rh(μ-OMe)(cod)]2 are used for the asymmetric hydroformylation of vinyl acetate. Enantiomeric excesses of up to 60% are achieved with regioselectivities of up to 99%. Only a BINAP/Rh ratio of 2 is required. Effects of pressure and temperature on catalyst stability, enantio- and chemoselectivity are discussed.
- Hoegaerts, Dirk,Jacobs, Pierre A.
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Read Online
- New diphosphite ligands for enantioselective asymmetric hydroformylation
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A series of new diphosphite ligands have been easily prepared from BINOL derivatives; moderate enantioselectivities (up to 80% ee) and excellent regioselectivities (b/l up to 98/2) have been achieved in the Rh-catalyzed asymmetric hydroformylation of vinyl acetate.
- Zou, Yaping,Yan, Yongjun,Zhang, Xumu
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Read Online
- Ferrocene-based bidentate phosphonite ligands for rhodium(I)-catalyzed enantioselective hydroformylation
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A new class of chiral modular bidentate phosphonite ligands has been synthesized in good overall yields by using cheap trans-1,2-diaminocyclohexane and ferrocene as starting materials, and applied in the Rh(I)-catalyzed asymmetric hydroformylation of vinyl acetate and styrene to afford the corresponding optically active aldehydes with good regioselectivity (up to 16.9 b/l ratio) and moderate to good enantioselectivity (up to 83% ee). The substituents on the backbone of the ligands are found to exhibit a remarkable effect on both the regio- and enantioselectivity of the catalysis.
- Peng, Xingao,Wang, Zheng,Xia, Chungu,Ding, Kuiling
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- Regioselective and rapid hydroformylation of vinyl acetate catalyzed by rhodium complex modified bulky phosphite ligand
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The regioselective hydroformylation of vinyl acetate catalyzed by rhodium complex of monodentate phosphite ligand, tri-1-naphthylphosphite P(ONp)3, was investigated. The P(ONp)3 ligand exhibited a considerable impact on the rate and selectivity of hydroformylation of vinyl acetate, notably high turnover frequency (up to 11,520 h-1) with excellent regioselectivity (99%) to the preferred branched aldehyde and high selectivity to aldehyde (93%). Significant results with the substrate having less reactive character toward hydroformylation and practically easy accessibility of the ligand (synthesized from inexpensive compound, 1-naphthol) make this system very attractive.
- Dabbawala, Aasif A.,Jasra, Raksh V.,Bajaj, Hari C.
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Read Online
- Tetradentate nitrogen phosphine ligand and preparation method and application thereof
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The invention provides a novel tetradentate nitrogen phosphine ligand as well as a preparation method and an application thereof in an unsaturated olefin hydroformylation reaction. The tetradentate nitrogen phosphine ligand is used for the hydroformylation reaction of olefin, so that the catalyst is more stable in the reaction, is not easy to inactivate at high temperature (more than 200 DEG C), the pressure of synthesis gas required by the reaction is lower, the reaction positive-to-negative ratio is improved, and the selectivity of a main product can be effectively improved.
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Paragraph 0057; 0060-0061
(2021/04/07)
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- Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
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The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application thereof, and avinyl acetate hydroformylation method. The phosphine ligand compound has a structure shown as a formula (1); wherein A is selected from a substituted or unsubstituted C1-C20 alkylene group; B1 and B2are each independently selected from a substituted or unsubstituted biphenyl group; substituent groups optionally existing in A, B1 and B2 are respectively and independently selected from at least oneof C1-C20 alkyl, halogen, C1-C10 alkoxyl, hydroxyl, carboxyl and aldehyde group; and the provided phosphine ligand compound can effectively improve the conversion rate of vinyl acetate and the selectivity of 2-acetoxy propionaldehyde.
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Paragraph 0103-0120
(2020/07/13)
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- Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof and vinyl acetate hydroformylation method (by machine translation)
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The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application of the phosphine ligand compound and vinyl acetate hydroformylation. The phosphine ligand compound has the structure shown in the formula (1); and A and B1 And B2 C is each independently selected from substituted or unsubstituted C1 - C20 Alkylene; and A, B1 And B2 The optionally present substituents are each independently selected from C. 1 - C20 Alkyl, halogen and C1 - C10 The phosphorus ligand compound provided by the invention can effectively improve the vinyl acetate conversion rate and 2 - acetoxy propionaldehyde selectivity. (by machine translation)
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Paragraph 0106-0127
(2020/07/13)
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- Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
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The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application thereof, and avinyl acetate hydroformylation method. The phosphine ligand compound has a structure shown as a formula (1); wherein A is selected from substituted or unsubstituted phenyl and substituted or unsubstituted biphenyl; B1 and B2 are each independently selected from a substituted or unsubstituted biphenyl group; substituent groups optionally existing in A, B1 and B2 are respectively and independently selected from at least one of C1-C20 alkyl, halogen, C1-C10 alkoxyl, hydroxyl, carboxyl and aldehyde group; and the provided phosphine ligand compound can effectively improve the conversion rate of vinyl acetate and the selectivity of 2-acetoxy propionaldehyde.
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Paragraph 0116-0117; 0132-0133; 0137
(2020/07/13)
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- Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof and vinyl acetate hydroformylation method (by machine translation)
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The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application of the phosphine ligand compound and vinyl acetate hydroformylation. The phosphine ligand compound has the structure shown in the formula (1); wherein A is selected from substituted or unsubstituted phenyl; B1 And B2 C is each independently selected from substituted or unsubstituted C1 - C20 Alkylene; A, B1 And B2 The optionally present substituents are each independently selected from C. 1 - C20 Alkyl, halogen and C1 - C10 The phosphorus ligand compound provided by the invention can effectively improve the vinyl acetate conversion rate and 2 - acetoxy propionaldehyde selectivity. (by machine translation)
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Paragraph 0094-0095; 0106-0107; 0111
(2020/07/13)
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- Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof and vinyl acetate hydroformylation method (by machine translation)
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The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application of the phosphine ligand compound and vinyl acetate hydroformylation. The phosphine ligand compound has the structure shown in formula (1); wherein A is selected from substituted or unsubstituted phenyl; R1 , R2 , R3 And R4 C is each independently selected from substituted or unsubstituted C1 - C20 Alkyl, substituted or unsubstituted phenyl; A, R1 , R2 , R3 And R4 The optionally present substituents are each independently selected from C. 1 - C20 Alkyl, halogen and C1 - C10 The phosphorus ligand compound provided by the invention can effectively improve the vinyl acetate conversion rate and 2 - acetoxy propionaldehyde selectivity. (by machine translation)
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Paragraph 0112-0117
(2020/07/13)
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- Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol
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The invention provides a tetradentate phosphine ligand, a preparation method of the tetradentate phosphine ligand, a hydroformylation catalyst, a reaction method of the hydroformylation catalyst and apreparation method of 1, 3-propylene glycol, and belongs to the technical field of compound materials. The general formula of the tetradentate phosphine ligand is shown in the specification, whereinR1 is hydrogen or halogen, R2 is a nitrogen-containing heterocyclic ring or a complex of the tetradentate phosphine ligand and a rhodium complex, can be used for carrying out a hydroformylation catalytic reaction, and can be used for preparing 1, 3-propylene glycol.
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Paragraph 0070-0073; 0081-0092
(2020/08/25)
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- Effector enhanced enantioselective hydroformylation
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In this communication, we report rhodium DIMPhos complexes with an integrated DIM-receptor that can bind carboxylate containing effectors and their application in the rhodium catalyzed hydroformylation reaction. The binding of chiral effectors in non-chiral [Rh(DIMPhos)] catalysts does not lead to enantioselective hydroformylation, but the binding of either achiral or chiral effectors can significantly enhance the enantioselectivity induced by the chiral Rh-metal complexes. For example, the supramolecular complex [Rh]/[1S?L3] displays high regio- and enantioselectivity in the hydroformylation of vinyl acetate (72% ee, and b/l >99), whereas in absence of this effector the ee is around 17%.
- Bai, Shao-Tao,Kluwer, Alexander M.,Reek, Joost N. H.
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supporting information
p. 14151 - 14154
(2019/12/02)
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- Hydroformylation method of vinyl acetate
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The invention relates to the field of hydroformylation of olefins, and discloses a hydroformylation method of vinyl acetate. The hydroformylation method comprises the steps that in the presence of a catalyst system, the vinyl acetate makes contact with carbon monoxide and hydrogen, the catalyst system comprises a rhodium complex and a phosphine ligand, the phosphine ligand is selected from at least one of phosphorus-containing organic matter shown in a formula (1) (please see the specifications for the formula), in the formula (1), A is selected from substituted or unsubstituted aryl groups oralkyl groups of C1-C10, and B is selected from hydrogen, halogen, acetyl and the like. According to the hydroformylation method, the high conversion rate can be ensured, meanwhile, the selectivity ofaldehyde can be improved, and 3-acetoxypropanal has the high relative content.
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Paragraph 0048-0069
(2019/11/12)
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- Backbone-Modified Bisdiazaphospholanes for Regioselective Rhodium-Catalyzed Hydroformylation of Alkenes
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A series of tetraaryl bisdiazaphospholane (BDP) ligands were prepared varying the phosphine bridge, backbone, and substituents in the 2- and 5-positions of the diazaphospholane ring. The parent acylhydrazine backbone was transformed to an alkylhydrazine via a borane reduction procedure. These reduced ligands contained an all sp3 hybridized ring mimicking the all sp3 phospholane of (R,R)-Ph-BPE, a highly selective ligand in asymmetric hydroformylation. The reduced bisdiazaphospholane (red-BDP) ligands were shown crystallographically to have an increased C-N-N-C torsion angle - this puckering resembles the structure of (R,R)-Ph-BPE and has a dramatic influence on regioselectivity in rhodium catalyzed hydroformylation. The red-BDPs demonstrated up to a 5-fold increase in selectivity for the branched aldehyde compared to the acylhydrazine parent ligands. This work demonstrates a facile procedure for increased branched selectivity from the highly active and accessible class of BDP ligands in hydroformylation.
- Wildt, Julia,Brezny, Anna C.,Landis, Clark R.
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p. 3142 - 3151
(2017/09/05)
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- Method for hydroformylation of vinyl acetate
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The invention relates to a method for hydroformylation of vinyl acetate. The method comprises the step of enabling the vinyl acetate to be in contact with carbon monoxide and hydrogen gas in the presence of a solvent and a catalyst system, wherein the catalyst system contains a rhodium complex and a phosphine ligand; the rhodium complex is one or more selected from rhodium(triphenylphosphine)carbonyl acetylacetonate, rhodium acetylacetone and chlorocarbonylbis(triphenylphosphine)rhodium; and the phosphine ligand is one or more selected from phosphine-containing organic matters represented by the following formulae shown in the description, wherein Ar in the formulae (1, 3 and 4) is substituted or unsubstituted aryl, M in the formula (2) is hydrogen, halogen element or substituted or unsubstituted alkyl, and t in the formula (3) is an integer from 2 to 10. According to the method, the selectivity to 3-acetoxypropanal in a hydroformylation reaction process of the vinyl acetate can be improved while a relatively high conversion ratio is guaranteed under the conditions of relatively low reaction temperature and reaction pressure.
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Paragraph 0052; 0053; 0054; 0055; 0056; 0057; 0058-0080
(2017/08/28)
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- Vinylacetate hydroformylation method
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The invention relates to a vinylacetate hydroformylation method. The vinylacetate hydroformylation method comprises the step that in the presence of a catalyst system, vinylacetate makes contact with carbonic oxide and hydrogen, and the catalyst system contains a rhodium complex which is at least one selected from rhodium(triphenylphosphine)carbonyl acetylacetonate, rhodium acetylacetonate and chlorocarbonylbis(triphenylphosphine)rhodium. With the adoption of the vinylacetate hydroformylation method provided by the invention, the high conversion rate of the vinylacetate can be ensured under the mild reaction condition, and the selectivity of 3-acetoxypropanal can be improved.
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Paragraph 0049; 0050; 0051; 0052; 0053; 0054; 0055-0072
(2017/08/28)
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- Method for hydroformylating vinyl acetate
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The invention discloses a method for hydroformylating vinyl acetate. The method is characterized in that vinyl acetate is in contact with carbon monoxide and hydrogen in the presence of a solvent and a catalyst, and the catalyst is one or more selected from acetylacetonatocarbonyltriphenylphosphine rhodium, rhodium acetylacetonate and carbonyltriphenylphosphine rhodium chloride. The method has the advantages of mild reaction conditions, guaranteeing of the high conversion rate of the vinyl acetate, and increase of the selectivity of 3-acetoxypropanal.
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Paragraph 0036; 0037; 0038; 0039; 0040; 0041; 0042-0053
(2017/08/28)
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- Tunable P-Chiral Bisdihydrobenzooxaphosphole Ligands for Enantioselective Hydroformylation
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Air-stable and tunable chiral bisdihydrobenzooxaphosphole ligands (BIBOPs) were employed in rhodium-catalyzed asymmetric hydroformylation of various terminal olefins with excellent conversions (>99%), moderate-to-excellent enantioselectivities (up to 95:5 er), and branched to linear ratios (b:l) of up to 400.
- Tan, Renchang,Zheng, Xin,Qu, Bo,Sader, C. Avery,Fandrick, Keith R.,Senanayake, Chris H.,Zhang, Xumu
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supporting information
p. 3346 - 3349
(2016/07/26)
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- Method used for producing 1,3-propanediol
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The invention relates to a method used for producing 1,3-propanediol. The invention mainly aims at solving problems of low activity and low selectivity of 1,3-propanediol catalysts in prior arts. The method mainly comprises the following steps: vinyl acetate is subjected to hydroformylation, such that 3-acetoxypropionaldehyde is obtained; 3-acetoxypropionaldehyde is hydrogenated, such that 3-acetoxypropanol is obtained; and 3-acetoxypropanol is subjected to alcoholysis, such that 1,3-propanediol is obtained. A hydroformylation catalyst comprises a main catalyst and an accelerant. The main catalyst comprises a carrier and an active component. The active component is a rhodium compound. The accelerant is at lease one selected from organic amine and organic phosphorus. The carrier is silicon dioxide which has an aluminum coating on the surface and which is modified with modification metal element. The modification metal element is at least one selected from IIB metal elements. With the technical scheme, the problem is well solved. The method can be applied in 1,3-propanediol industrial production.
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Paragraph 0174
(2016/11/28)
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- Method for producing 1,3-propylene glycol from vinyl acetate
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The invention relates to a method for producing 1,3-propylene glycol from vinyl acetate to mainly solve the problems of relatively low catalyst activity and selectivity of 1,3-propylene glycol in the prior art. By adoption of the technical scheme that the preparation method of 1,3-propylene glycol comprises the following steps: carrying out hydroformylation on vinyl acetate to obtain 3-acetoxypropanal, carrying out hydrogenation on 3-acetoxypropanal to obtain 3-acetoxypropanol, and hydrolyzing 3-acetoxypropanol to obtain 1,3-propylene glycol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and the active components comprise at least one of iron series elements, an alkaline earth metal element, and at least one metal element selected from IVA and IIB, the technical problems are well solved, and the method can be used for industrial production of 1,3-propylene glycol.
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Paragraph 0163
(2016/11/28)
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- Preparation method of 1,3-propylene glycol
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The invention relates to a preparation method of 1,3-propylene glycol and mainly solves the problem of low activity and selectivity of a 1,3-propylene glycol catalyst in the prior art. The preparation method includes the following steps: 1) performing hydroformylation to vinyl acetate to prepare 3-acetoxylpropyl aldehyde; 2) hydrogenating the 3-acetoxylpropyl aldehyde to prepare 3-acetoxylpropyl alcohol; and 3) hydrolyzing the 3-acetoxylpropyl alcohol to obtain the 1,3-propylene glycol. A catalyst for the hydroformylation is prepared with SiO2, Al2O3 or a mixture thereof as a carrier with active components including rhodium, lanthanum-series metals, and at least one metal element selected from the groups of IVA and VIB. The method solves the technical problem well and is used for industrial production of the 1,3-propylene glycol.
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Paragraph 0179
(2016/11/28)
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- 1,3-propanediol synthesis method
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The invention relates to a 1,3-propanediol synthesis method. The invention mainly aims at solving the problems of low activity and low selectivity of 1,3-propanediol catalyst in prior arts. The 1,3-propanediol synthesis method comprises the following steps: vinyl acetate is subjected to hydroformylation, such that 3-acetoxypropionaldehyde is obtained; 3-acetoxypropionaldehyde is hydrogenated, such that 3-acetoxypropanol is obtained; and 3-acetoxypropanol is subjected to alcoholysis, such that 1,3-propanediol is obtained. A hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and active components comprise at least one selected from iron-series elements, alkali metal element and at least one metal element selected from VA and IB. With the above technical scheme, the technical problem is well solved. The method can be applied in 1,3-propanediol industrial production.
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Paragraph 0198
(2016/11/28)
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- 1,3-propanediol production method
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The invention relates to a 1,3-propanediol production method. The invention mainly aims at solving the problems of low activity and low selectivity of 1,3-propanediol catalyst in prior arts. The 1,3-propanediol production method comprises the following steps: vinyl acetate is subjected to hydroformylation, such that 3-acetoxypropionaldehyde is obtained; 3-acetoxypropionaldehyde is hydrogenated, such that 3-acetoxypropanol is obtained; and 3-acetoxypropanol is hydrolyzed, such that 1,3-propanediol is obtained. A hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and active components comprise rhodium, alkaline earth metal and at least one metal element selected from VA and IVB. With the above technical scheme, the technical problem is well solved. The method can be applied in 1,3-propanediol industrial production.
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Paragraph 178
(2016/12/01)
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- Method for preparing 1,3-propanediol from vinyl acetate
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The invention relates to a method for preparing 1,3-propanediol from vinyl acetate. The method is mainly used for solving the problem in the prior art that 1,3-propanediol catalysts are relatively low in activity and selectivity. Through adopting the technical scheme that the method for preparing 1,3-propanediol comprises the following steps: subjecting vinyl acetate to hydroformylation, so as to obtain 3-acetoxypropanal; hydrogenating 3-acetoxypropanal, so as to obtain 3-acetoxypropanol; and hydrolyzing 3-acetoxypropanol so as to obtain 1,3-propanediol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture of SiO2 and Al2O3 as a carrier, and active ingredients comprise at least one element selected from ferrous elements, at least one element selected from metalloid elements and at least one metal element selected from VB and alkali metal elements, the technical problem is better solved, and the method can be applied to the industrial production of 1,3-propanediol.
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Paragraph 0188
(2016/12/01)
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- Synthetic method for 1,3-propylene glycol through hydroformylation of vinyl acetate
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The invention relates to a synthetic method for 1,3-propylene glycol through hydroformylation of vinyl acetate, and is mainly to solve the problem of low activity and selectivity of a 1,3-propylene glycol catalyst. According to a technical scheme of the invention, the preparation method for 1,3-propylene glycol comprises the following steps: subjecting vinyl acetate to hydroformylation so as to obtain 3-acetoxyl propionaldehyde, subjecting 3-acetoxyl propionaldehyde to hydrogenation so as to obtain 3-acetoxyl propanol, and subjecting 3-acetoxyl propanol to hydrolysis so as to obtain 1,3-propylene glycol, wherein a hydroformylation catalyst uses SiO2, Al2O3 or a mixture of SiO2 and Al2O3 as a carrier, and an active component comprises at least one selected from the group consisting of iron series elements, at least one selected from the group consisting of metalloid elements, and at least one metal element selected from the group consisting of group-VIB and alkaline-earth metals; thus, the above-mentioned technical problem is well solved, and the synthetic method can be applied in industrial production of 1,3-propylene glycol.
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Paragraph 0196
(2016/12/01)
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- Preparation of 1,3-propanediol used by the method of (by machine translation)
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The present invention relates to preparation of 1.3-propanediol method used, mainly solves the problems in the prior art 1.3-propanediol the activity of the catalyst and the problem of low selectivity, by the method for preparation of 1.3-propanediol, comprising the following steps: obtaining ethylene hydroformylation of acetic acid 3-acetoxy-propionaldehyde; 3-acetoxy-propionaldehyde hydrogenation to obtain 3-acetoxy-propanol; 3-acetoxy-propanol alcoholysis was 1.3-propanediol; the hydroformylation catalysts SiO 2, Al 2 O 3 or mixtures thereof as a carrier, the active component includes rhodium, lanthanide series metal elemental IVA and VIB and is selected from at least one of the technical scheme of the metal elements, better solves the technical problem of, can be used for the 1.3-propanediol in the industrial production. (by machine translation)
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Paragraph 0179
(2016/12/01)
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- Method for preparing 1, 3-propanediol through hydroformylation of vinyl acetate
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The invention relates to a method for preparing 1, 3-propanediol through hydroformylation of vinyl acetate. The method mainly solves the problem that the prior art has low 1, 3-propanediol catalyst activity and low selectivity. The method provided through the invention comprises vinyl acetate hydroformylation for 3-acetoxypropanal preparation, 3-acetoxypropanal hydrogenation for 3-acetoxypropanol preparation and 3-acetoxypropanol hydrolysis for 1, 3-propanediol preparation. A hydroformylation catalyst utilizes SiO2, Al2O3 or their mixture as a carrier and active ingredients comprise at least one of platinum metal elements, at least one of alkaline-earth metal elements and at least one of VB and IVA metals. The method well solves the above technical problem and can be used for 1, 3-propanediol industrial production.
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Paragraph 0196
(2016/12/01)
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- Method for producing 1,3-propanediol
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The invention relates to a method for producing 1,3-propanediol. The method is mainly used for solving the problem in the prior art that 1,3-propanediol catalysts are relatively low in activity and selectivity. Through adopting the technical scheme that the method for producing 1,3-propanediol comprises the following steps: subjecting vinyl acetate to hydroformylation, so as to obtain 3-acetoxypropanal; hydrogenating 3-acetoxypropanal, so as to obtain 3-acetoxypropanol; and hydrolyzing 3-acetoxypropanol so as to obtain 1,3-propanediol, wherein a hydroformylation catalyst comprises a main catalyst and an accelerant, the main catalyst comprises a carrier and an active ingredient, the active ingredient is a compound of rhodium, the accelerant is at least one of organic amine and organophosphorus, the carrier is modifying metal element modified silica, of which the surface contains an aluminum coating, and a modifying metal element is at least one element selected from IIB metal elements, the problem is better solved, and the method can be applied to the industrial production of 1,3-propanediol.
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Paragraph 0029; 0038; 0048; 0058; 0069; 0080; 0090
(2016/12/01)
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- Method for preparing 1,3-propylene glycol
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The invention relates to a method for preparing 1,3-propylene glycol to mainly solve the problems of low yield and selectivity of 1,3-propylene glycol in the process of preparing 1,3-propylene glycol from vinyl acetate according to a route of carrying out hydroformylation at first, then carrying out hydrogenation, and finally carrying out hydrolysis. By adoption of the technical scheme that the method for preparing 1,3-propylene glycol comprises the following steps: carrying out hydroformylation on vinyl acetate to obtain 3-acetoxypropanal, carrying out hydrogenation on 3-acetoxypropanal to obtain 3-acetoxypropanol, and carrying out hydrolysis on 3-acetoxypropanol to obtain 1,3-propylene glycol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and the active components comprise rhodium, lanthanide series metal elements, and at least one metal element selected from VA and VB, the technical problems are well solved, and the method can be used for industrial production of 1,3-propylene glycol.
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Paragraph 0178
(2016/12/01)
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- Method for synthesizing 1,3-propanediol from vinyl acetate
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The invention relates to a method for synthesizing 1,3-propanediol from vinyl acetate. The method is mainly used for solving the problem in the prior art that 1,3-propanediol catalysts are relatively low in activity and selectivity. Through adopting the technical scheme that the method for synthesizing 1,3-propanediol from vinyl acetate comprises the following steps: subjecting vinyl acetate to hydroformylation, so as to obtain 3-acetoxypropanal; hydrogenating 3-acetoxypropanal, so as to obtain 3-acetoxypropanol; and hydrolyzing 3-acetoxypropanol so as to obtain 1,3-propanediol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture of SiO2 and Al2O3 as a carrier, and active ingredients comprise at least one element selected from ferrous elements, an alkali metal element and at least one metal element selected from VA and IB elements, the technical problem is better solved, and the method can be applied to the industrial production of 1,3-propanediol.
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Paragraph 197
(2016/12/01)
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- Method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate
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The invention relates to a method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate to mainly solve the problems of relatively low catalyst activity and selectivity of 1,3-propylene glycol in the prior art. By adoption of the technical scheme that the preparation method of 1,3-propylene glycol comprises the following steps: carrying out hydroformylation on vinyl acetate to obtain 3-acetoxypropanal, carrying out hydrogenation on 3-acetoxypropanal to obtain 3-acetoxypropanol, and hydrolyzing 3-acetoxypropanol to obtain 1,3-propylene glycol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and the active components comprise at least one of platinum group metal elements, at least one of alkali metal elements, and at least one metal element selected from VIIB and VA metals, the technical problems are well solved, and the method can be used for industrial production of 1,3-propylene glycol.
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Paragraph 0194
(2016/12/22)
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- Method for producing 1, 3-propanediol
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The invention relates to a method for producing 1, 3-propanediol. The method mainly solves the problem that the prior art for preparing 1, 3-propanediol through vinyl acetate hydroformylation, hydrogenation and hydrolysis has a low yield and low selectivity. The method provided through the invention comprises vinyl acetate hydroformylation for 3-acetoxypropanal preparation, 3-acetoxypropanal hydrogenation for 3-acetoxypropanol preparation and 3-acetoxypropanol alcoholysis for 1, 3-propanediol preparation. A hydroformylation catalyst utilizes SiO2, Al2O3 or their mixture as a carrier and active ingredients comprise rhodium and lanthanide metal elements and at least one of VA and VB metals. The method well solves the technical problem and can be used for 1, 3-propanediol industrial production.
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Paragraph 0175; 0176; 0177; 0178; 0179; 0180
(2017/01/02)
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- Supramolecularly Regulated Ligands for Asymmetric Hydroformylations and Hydrogenations
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Herein we report the use of polyether binders as regulation agents (RAs) to enhance the enantioselectivity of rhodium-catalyzed transformations. For reactions of diverse substrates mediated by rhodium complexes of the α,ω-bisphosphite-polyether ligands 1-5,a-d, the enantiomeric excess (ee) of hydroformylations was increased by up to 82 (substrate: vinyl benzoate, 96ee), and the ee value of hydrogenations was increased by up to 5 (substrate: N-(1-(naphthalene-1-yl)vinyl)acetamide, 78ee). The ligand design enabled the regulation of enantioselectivity by generation of an array of catalysts that simultaneously preserve the advantages of a privileged structure in asymmetric catalysis and offer geometrically close catalytic sites. The highest enantioselectivities in the hydroformylation of vinyl acetate with ligand 4b were achieved by using the Rb[B(3,5-(CF3)2C6H3)4] (RbBArF) as the RA. The enantioselective hydrogenation of the substrates 10 required the rhodium catalysts derived from bisphosphites 3a or 4a, either alone or in combination with different RAs (sodium, cesium, or (R,R)-bis(1-phenylethyl)ammonium salts). This design approach was supported by results from computational studies.
- Vidal-Ferran, Anton,Mon, Ignasi,Bauzá, Antonio,Frontera, Antonio,Rovira, Laura
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supporting information
p. 11417 - 11426
(2015/08/03)
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- Asymmetric Hydroformylation of Heterocyclic Olefins Mediated by Supramolecularly Regulated Rhodium-Bisphosphite Complexes
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Rhodium complexes derived from conformationally transformable α,ω-bisphosphite ligands combined with a suitable alkali metal BArF salt as a regulation agent (RA) provide high regio- and enantioselectivities in the asymmetric hydroformylation (AHF) of three heterocyclic olefins. The outcome of the AHF could be exquisitely regulated by choosing the appropriate RA with an increase in the ee, the reversal of the regioselectivity, or the complete suppression of one byproduct.
- Rovira, Laura,Vaquero, Mónica,Vidal-Ferran, Anton
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supporting information
p. 10397 - 10403
(2015/11/03)
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- Easily accessible and highly tunable bisphosphine ligands for asymmetric hydroformylation of terminal and internal alkenes
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An efficient methodology for synthesizing a small library of easily tunable and sterically bulky ligands for asymmetric hydroformylation (AHF) has been reported. Five groups of alkene substrates have been tested with excellent conversions, moderate-to-excellent regio- and enantioselectivities. Among the best result of the reported literature, application of ligand 1 c in the highly selective AHF of the challenging substrate 2,5-dihydrofuran yielded almost one isomer in up to 99 % conversion along with enantiomeric excesses (ee) of up to 92 %. Highly enantioselective AHF of dihydropyrrole substrates is achieved using the same ligand, with up to 95 % ee and up to >1:50 β-isomer/α- isomer ratio. The simpler the better! An efficient method for the easy and tunable synthesis of a series of asymmetric hydroformylation (AHF) ligands from low-cost, commercially available starting materials has been reported. These ligands can give excellent conversions and moderate to excellent regio- and enantioselectivities for a broad range of mono- and disubstituted alkenes with a low catalyst loading (substrate-to-catalyst ratios (S/C) of 1000:1 to 3000:1).
- Xu, Kun,Zheng, Xin,Wang, Zhiyong,Zhang, Xumu
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p. 4357 - 4362
(2014/05/06)
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- Immobilized bisdiazaphospholane catalysts for asymmetric hydroformylation
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Condensation reactions of enantiopure bis-3,4-diazaphospholanes (BDPs) that are functionalized with carboxylic acids enable covalent attachment to bead and silica supports. Exposure of tethered BDPs to the hydroformylation catalyst precursor, Rh(acac)(CO)2, yields catalysts for immobilized asymmetric hydroformylation (iAHF) of prochiral alkenes. Compared with homogeneous catalysts, catalysts immobilized on Tentagel resins exhibit similarly high regioselectivity and enantioselectivity. When corrected for apparent catalyst loading, the activity of the immobilized catalysts approaches that of the homogeneous analogues. Excellent recyclability with trace levels of rhodium leaching are observed in batch and flow reactor conditions. Silica-bound catalysts exhibit poorer enantioselectivities.
- Adint, Tyler T.,Landis, Clark R.
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p. 7943 - 7953
(2014/06/23)
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- 1,1-P-OP ligands with P-stereogenic phosphino groups in asymmetric hydrogenations and hydroformylations
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A new series of narrow-bite-angle phosphine-phosphite (1,1-P-OP) ligands (3a-d) has been efficiently prepared from the enantiopure (SP)-tert- butyl(hydroxymethyl)methylphosphino borane complex 1, a crucial intermediate. The catalytic performance of the ligands in Rh-mediated asymmetric hydrogenations and hydroformylations is described. The corresponding rhodium complexes provided excellent efficiencies (full conversion in all cases) and high enantioselectivities (up to 98% ee) for the asymmetric hydrogenation of structurally diverse functionalized alkenes. Furthermore, rhodium catalysts derived from these 1,1-P-OP ligands were highly active and gave excellent regioselectivities (branched/linear product ratios of up to 97/3) and moderate enantioselectivities in the hydroformylation of different terminal olefins.
- Lao, Joan R.,Benet-Buchholz,Vidal-Ferran, Anton
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p. 2960 - 2963
(2014/07/08)
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- Enantiopure narrow bite-angle P-OP ligands: Synthesis and catalytic performance in asymmetric hydroformylations and hydrogenations
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Herein is reported the preparation of a set of narrow bite-angle P-OP ligands the backbone of which contains a stereogenic carbon atom. The synthesis was based on a Corey-Bakshi-Shibata (CBS)-catalyzed asymmetric reduction of phosphomides. The structure of the resulting 1,1-P-OP ligands, which was selectively tuned through adequate combination of the configuration of the stereogenic carbon atom, its substituent, and the phosphite fragment, proved crucial for providing a rigid environment around the metal center, as evidenced by X-ray crystallography. These new ligands enabled very good catalytic properties in the Rh-mediated enantioselective hydrogenation and hydroformylation of challenging and model substrates (up to 99 % ee). Whereas for asymmetric hydrogenation the optimal P-OP ligand depended on the substrate, for hydroformylation, a single ligand was the highest-performing one for almost all studied substrates: it contains an R-configured stereogenic carbon atom between the two phosphorus ligating groups, and an S-configured 3,3′-diphenyl-substituted biaryl unit. Ligand design: Narrow-bite-angle P-OP ligands incorporating a stereogenic carbon atom in their backbone have been synthesized by Corey-Bakshi-Shibata (CBS)-catalyzed asymmetric reduction of the corresponding intermediates followed by O-phosphorylation. Rhodium complexes of these ligands provided very good catalytic performance in hydroformylations and hydrogenations (see scheme).
- Fernández-Pérez, Héctor,Benet-Buchholz, Jordi,Vidal-Ferran, Anton
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p. 15375 - 15384
(2016/02/18)
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- Hydroformylation of styrene, vinyl acetate and allyl cyanide with air-stable rhodium catalysts ligated by C2-symmetric bis-N-heterocyclic carbenes
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This investigation describes an experimental examination of a new family of chiral rhodium complexes towards catalytic enantioselective hydroformylation. Both free bis-N-heterocyclic carbene and enetetramine ligand precursors are used to metallate Rh(I) salts under mild conditions. All catalysts prepared exhibit high conversion and regioselectivity for three substrates (styrene, vinyl acetate, allyl cycanide) but poor enantioselectivity.
- Tariq Jan, Muhammad,Ali, Shaukat,Ahmad, Shabir,Abdel-Reheem, Mohammed A. T.,Hussain, Iqbal,Ullah, Riaz
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p. 6911 - 6914
(2015/02/19)
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- Libraries of bisdiazaphospholanes and optimization of rhodium-catalyzed enantioselective hydroformylation
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Twelve chiral bis-3,4-diazaphospholane ligands and six alkene substrates (styrene, vinyl acetate, allyloxy-tert-butyldimethylsilane, (E)-1-phenyl-1,3- butadiene, 2,3-dihydrofuran, and 2,5-dihydrofuran) probe the influence of steric bulk on the activity and selectivity of asymmetric hydroformylation (AHF) catalysts. Reaction of an enantiopure bisdiazaphospholane tetraacyl fluoride with primary or secondary amines yields a small library of tetracarboxamides. For all six substrates, manipulation of reaction conditions and bisdiazaphospholane ligands enables state-of-the-art performance (90% or higher ee, good regioselectivity, and high turnover rates). For the nondihydrofuran substrates, the previously reported ligand, (S,S)-2, is generally most effective. However, optimal regio- and enantioselective hydroformylation of 2,3-dihydrofuran (up to 3.8:1 α-isomer/β-isomer ratio and 90% ee for the α-isomer) and 2,5-dihydrofuran (up to 1:30 α-isomer/β- isomer ratio and 95% ee for the β-isomer) arises from bisdiazaphospholanes containing tertiary carboxamides. Hydroformylation of either 2,3- or 2,5-dihydrofuran yields some of the β-formyl product. However, the absolute sense of stereochemistry is inverted. A stereoelectronic map rationalizes the opposing enantiopreferences
- Adint, Tyler T.,Wong, Gene W.,Landis, Clark R.
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p. 4231 - 4238
(2013/06/05)
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- Small bite-angle P-OP ligands for asymmetric hydroformylation and hydrogenation
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A series of small bite-angle phosphine-phosphite (P-OP) ligands have been synthesized by a two-step method. The key intermediate was prepared by an unprecedented asymmetric carbonyl reduction of a phosphamide using the CBS (Corey-Bakshi-Shibata) catalyst. The topology of these ligands (a configurationally stable stereogenic carbon with two heteroatom substituents) and their small bite-angle (created by the close proximity of the two ligating groups to the metal center) together provide a rigid asymmetric environment around this center, enabling high stereoselectivity in hydroformylations and hydrogenations of standard substrates.
- Fernandez-Perez, Hector,Benet-Buchholz,Vidal-Ferran, Anton
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supporting information
p. 3634 - 3637
(2013/08/23)
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- Bis(phosphite) ligands with distal regulation: Application in rhodium-mediated asymmetric hydroformylations
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Small amounts of achiral polyether binders are employed to enhance the enantioselectivity of the hydroformylation of an array of diversely substituted substrates (increase of up to 62 % ee for vinyl acetate) mediated by chiral rhodium complexes derived from the α,ω-bis(phosphite)-polyether ligands 1. To the best of our knowledge, this study represents an unprecedented successful example of the positive regulation of enantioselectivity in hydroformylations.
- Mon, Ignasi,Jose, D. Amilan,Vidal-Ferran, Anton
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supporting information
p. 2720 - 2725
(2013/04/10)
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- AMIDO-FLUOROPHOSPHITE COMPOUNDS AND CATALYSTS
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Amido-fluorophosphite compounds and catalyst systems comprising at least one amido-fluorophosphite ligand compound in combination with a transition metal are described. Moreover, the use of amido-fluorophosphite containing catalysts for transition metal catalyzed processes, especially to the hydroformylation of various olefins to produce aldehydes are also described.
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Page/Page column 26
(2013/03/26)
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- Room temperature ambient pressure (RTAP)-hydroformylation in water using a self-assembling ligand
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We herein demonstrate a hydroformylation at room temperature and ambient pressure (RTAP) using our Rh/6-DPPon (1) system in aqueous media. The hydrogen bonding network of the ligand backbone stays intact, exemplified by the excellent regioselectivity for the linear aldehyde. Various substrates with different functional groups (with some prone to hydrolysis) are stable under the applied conditions and can undergo hydroformylation resulting in good yields. Copyright
- Straub, Alexander T.,Otto, Marina,Usui, Ippei,Breit, Bernhard
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supporting information
p. 2071 - 2075
(2013/08/23)
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- New tetraphosphorus ligands for highly linear selective hydroformylation of allyl and vinyl derivatives
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New tetraphosphorus ligands have been developed and applied in the rhodium-catalyzed regioselective hydroformylation of a variety of functionalized allyl and vinyl derivatives. Remarkably high linear selectivity was obtained by these tetraphosphorus ligands. The ligand that bears strong electron-withdrawing 2,4-difluorophenyl groups is the most effective one in affording linear aldehydes. The Rh/tetraphosphorus ligand catalyst is highly effective to produce linear aldehydes from functionalized allyl derivatives with heteroatoms or aromatic groups directly adjacent to the allyl group. For vinyl derivatives, the ligand is highly linear selective for acrylic derivatives, styrene, vinyl pyridine, and vinyl phthalimide. Linear to branch ratios of 26:1 and 10:1 were obtained for the hydroformylation of styrene and allyl cyanide, respectively. New tetraphosphorus ligands have been developed and applied in the rhodium-catalyzed regioselective hydroformylation of a variety of allyl and vinyl olefins (see scheme). Remarkably high linear selectivities were obtained by these ligands. Linear-to-branch ratios of 26:1 and 10:1 were obtained for the hydroformylation of styrene and allyl cyanide, respectively. Copyright
- Cai, Chaoxian,Yu, Shichao,Cao, Bonan,Zhang, Xumu
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experimental part
p. 9992 - 9998
(2012/09/07)
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- Helicene-based phosphite ligands in asymmetric transition-metal catalysis: Exploring Rh-catalyzed hydroformylation and Ir-catalyzed allylic amination
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Starting from the optically pure [6]helicene-like alcohol(P,3S)-3-methyl-4- (4-methylphenyl)-1,3,6,7-tetrahydrobenzo[c]benzo[5,6]phenanthro[4,3-e] oxepin-14-ol, four helical phosphites were prepared from the corresponding chlorophosphites. These ligands containing parent or substituted 1,3,2-dioxaphospholan-2-yl or dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl moieties were applied to the asymmetric hydroformylation of terminal alkenes catalyzed by Rh(acac)(CO)2 and the asymmetric allylic amination of cinnamyl-type carbonates catalyzed by [Ir(cod)Cl]2. The helical phosphite containing the dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl group was most successful in the asymmetric hydroformylation of styrene, leading to moderate enantiomeric excess values (up to 32 % ee), high regioselectivity in favor of the branched product, and mostly high conversion, whereas the helical ligand containing the 4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yl fragment was most effective in asymmetric allylic aminations, exhibiting high enantioselectivity (up to 94 % ee), excellent regioselectivity in favor of the branched products, and good reactivity. This study represents the first use of helicene-like ligands in asymmetric reactions, including hydroformylation and allylic amination, and the promising results indicate the potential of the helicene moieties as chiral inductors. Copyright
- Krausova, Zuzana,Sehnal, Petr,Bondzic, Bojan P.,Chercheja, Serghei,Eilbracht, Peter,Stara, Irena G.,Saman, David,Stary, Ivo
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experimental part
p. 3849 - 3857
(2011/09/12)
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- Transformations of chromanol and tocopherol and synthesis of ascorbate conjugates
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α-Tocopherol and as a model compound pentamethylchromanol could be transferred into simple and more complex 5a-ether derivatives including galactopyranose as well as ascorbic acid conjugates. Following elaboration of a glucopyranoside spacer element this could be used for tethering the vitamin E and the vitamin C components to give novel conjugates for subsequent biostudies concerning their proposed synergism of antioxidant properties in tissues.
- Lahmann, Martina,Thiem, Joachim
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experimental part
p. 1654 - 1664
(2011/04/18)
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- TRIPHENYLPHOSPHINE DERIVATIVES
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The present invention relates to a triphenylphosphine of Formula (I) wherein M is a proton or a monovalent or divalent cation, n is an integer selected from 1 and 2, p takes a value selected from 1/2, 1 and 2, R1 is selected from H, C1-C18 alkyl, CF3 and SO3-, R11, R12 and R13 are independently selected from H and C1-C18 alkyl, with the proviso that if R1 is SO3-, then the product of n and p is equal to 2, R2, R3 and R5 are independently selected from H and C1-C18 alkyl, R4 is H, R6-R10 are independently selected from H, C1-C18 alkyl and CF3, at least one of R6-R10 being CF3; if R1 is not SO3-, then the product of n and p is equal to 1, R1-R10 are independently selected from H, C1-C18 is alkyl and CF3, at least one of the groups R1 -R10 being CF3; the present invention also is directed to a process for obtaining a triphenyl phosphine of Formula (I) and its use as ligand in the catalysis field and other several applications.
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Page/Page column 31; 32
(2011/05/05)
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- Rhodium-catalyzed asymmetric hydroformylation with taddol-based indolphos ligands
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A small library of Taddol-based IndolPhos ligands 2a-g and their use in asymmetric hydroformylation (AHF) reactions are reported. Moderate to good enantioselectivities are obtained for styrene, vinyl acetate, and allyl cyanide up to 72%, 74%, and 63% ee, respectively. High b/l ratios are obtained, which results in a high net yield of the desired chiral aldehyde. An unprecedented temperature-dependent reversal of enantioselectivity is found when using ligands 2d,e, which are based on a xylyl-derived Taddol in the Rh-catalyzed AHF of styrene. Furthermore, these ligands give the opposite enantiomer of the product for vinyl acetate and allyl cyanide when compared to the other library members, all of which are based on (R,R)-tartaric acid. Ligands 2a and 2d display a similar kinetic profile, which is best described by type I kinetics. Deuterioformylation experiments have shown that insertion of the alkene into the Rh-H bond is irreversible under the conditions applied. High-pressure NMR studies indicate that the hydridobiscarbonyl rhodium species, which is the resting state of the catalyst, features equatorial-apical coordination of the ligands with a preference for the phosphine on the apical position, isomer A. However, in the case of ligand 2d the isomer in which the phosphoramidite occupies the apical position, B, is only marginally higher in free energy than isomer A. It is proposed that formation of the product takes place via isomer B for ligands 2d,e and via isomer A for all other ligands, explaining the observed reversal of enantioselectivity.
- Wassenaar, Jeroen,De Bruin, Bas,Reek, Joost N. H.
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experimental part
p. 2767 - 2776
(2010/08/06)
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- Isostructural phosphine-phosphite ligands in rhodium-catalyzed asymmetric hydroformylation
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Isostructural phosphine-phosphite ligands 7-10 have been synthesized from the condensation of chiral 3,3′-bis(trialkylsilyl)-2,2′-bisnaphthol phosphorochloridites and phenol-phosphanes 3-6. These ligands were evaluated as chiral inducers in the rhodium-catalyzed asymmetric hydroformylation reaction (AHF) of vinyl acetate and a series of styrene derivatives. The highest enantioselectivity, 78% ee, was observed in the AHF of vinyl acetate using phenylphosphino-based ligand 10. A direct correlation between the enantioselectivity and the Hammett constant σ of the substituent in the substrates was found (4-Me-styrene, 15% ee; styrene, 23% ee; 4-Cl-styrene, 51% ee) under mild reaction conditions for phenylphosphole-based ligand 8. Several rhodium-hydride and rhodium-acyl complexes were prepared and characterized by HP-NMR and HP-IR spectroscopy. Rhodium-hydride complexes of the formula [HRh(L)(CO)2] A with ligands 7, 8, and 10 were found to be highly conformationally fluxional in solution. The reaction of 4-Cl-styrene with rhodium-hydride complexes of ligands 7 and 8 gave the corresponding rhodium-acyl derivatives [(RCO)Rh(CO)2(L)] E. A comparative analysis of the spectroscopic properties of these rhodium-acyl complexes revealed that [(RCO)Rh(CO)2(7)] was more conformationally labile than [(RCO)Rh(CO)2(8)].
- Doro, Franco,Reek, Joost N. H.,Van Leeuwen, Piet W. N. M.
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experimental part
p. 4440 - 4447
(2011/01/06)
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- Efficient platinum(II) catalyzed hydroformylation reaction in water: Unusual product distribution in micellar media
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The hydroformylation of a variety of terminal and internal alkenes is efficiently performed by cationic platinum triflate complexes of the type [P2Pt(H2O)2](OTf)2 under mild conditions in an aqueous micellar medium. The use of surfactants is essential to ensure dissolution of the catalyst and substrate in water with catalysts being positioned on the anionic surface of the micelles. Aldehydes are obtained with linear to branched ratios up to >99:1. With styrene derivatives also the corresponding benzaldehydes are formed. The catalyst can be separated by extraction of the organic products with hexane and recycled for at least four times with only a modest loss of activity and no effect on selectivity.
- Gottardo, Marina,Scarso, Alessandro,Paganelli, Stefano,Strukul, Giorgio
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experimental part
p. 2251 - 2262
(2010/12/25)
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- Synthesis and application of modular phosphine-phosphoramidite ligands in asymmetric hydroformylation: Structure-selectivity relationship
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A series of hybrid phos- phine-phosphoramidite ligands has been designed and synthesized in moderate yields from chiral BINOL (1, 1′- bi-2-naphthol) or NOBIN (2-amino-2′- hydroxy-1, 1′-binaphthyl). They have achieved highly regio- and enantiose- lectivities in Rh-catalyzed asymmetric hydroformylations of styrene derivatives (branched/linear ratio up to 56.6, ee up to 99%), vinyl acetate derivatives (up to 98% ee), and allyl cyanide (up to 96 % ee). Systematic variation of ligand structure showed that the steric factor on the phsophoramidite moiety determined the performance of the ligand. With the increased hindrance, the branched/linear ratio rose, while the ee value dropped in the hydrofor- mylation of styrene. However, the N- substituents did not influence the selec- tivities much.
- Zhang, Xiaowei,Cao, Bonan,Yan, Yongjun,Yu, Shichao,Ji, Baoming,Zhang, Xumu
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experimental part
p. 871 - 877
(2010/06/20)
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- A highly diastereoselective route to dinaphtho [c,e][1,2] oxaphosphinines and their application as ligands in homogeneous catalysis
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A new and facile method for the synthesis of 6H-dinaphtho[c,e][1,2] oxaphosphinines starting from dinaphthol (BINOL) is described. The ring-opening of an intermediary dinaphtho[2,1-b;1′,2′-d]furan proceeds with extremely high diastereoselectivity and forms the thermodynamically most stable product. The stereochemistry was elucidated by 31P NMR spectroscopy and X-ray structural analysis. Epimerization at the stereogenic P-centre did not take place. DFT calculations were performed to determine the dihedral angles of several dinaphtho[c,e][1,2]oxaphosphinines and to explain the observed loss of stereochemistry during the total synthesis from, the starting enantiopure BINOL. The synthetic potential of 6-chloro-6H-dinaphtho[c,e][1,2]oxaphosphinine was corroborated in its reactions with phenols to afford the corresponding phosphonites. These were successfully applied as ligands in the Rh-catalysed hydroformylation of three terminal olefins.
- Shuklov, Ivan A.,Dubrovina, Natalia V.,Jiao, Haijun,Spannenberg, Anke,Boerner, Armin
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experimental part
p. 1669 - 1680
(2010/07/04)
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