104-54-1Relevant articles and documents
Catalytic hydrosilylation of carbonyl compounds by hydrido thiophenolato iron(II) complexes
Xue, Benjing,Sun, Hongjian,Niu, Qingfen,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
, p. 23 - 28 (2017)
The hydrosilylation of aldehydes and ketones under mild conditions with hydrido thiophenolato iron(II) complexes [cis–Fe(H)(SAr)(PMe3)4] (1–4) as catalysts is reported using (EtO)3SiH as an efficient reducing agent in the yields up to 95%. Among them complex 1 is the best catalyst. Complex 1 could also be used as catalyst to reduce the α,β-unsaturated carbonyl compounds selectively to the α,β-unsaturated alcohols in high yields.
Zn(BH4)2/ultrasonic irradiation: An efficient system for reduction of carbonyl compounds to their corresponding alcohols
Fanari, Siamak,Setamdideh, Davood
, p. 695 - 697 (2014)
Zn(BH4)2 under ultrasonic irradiation is an efficient reducing system in CH3CN. This system reduces a variety of carbonyl compounds to their corresponding alcohols at room temperature in high to excellent yields of the products. Also, a,b-unsaturated aldehydes and ketones was regioselectively reduced to the corresponding allylic alcohols.
Conversion of alkyl halides into the corresponding alcohols under mild reaction conditions
Ruddick, Clare L.,Hodge, Philip,Houghton, Mark P.
, p. 1359 - 1362 (1996)
Reaction of primary, cyclopentyl, allyl and arylmethyl halides, but not an acyclic secondary halide or a tertiary halide, in acetone or tetrahydrofuran with the formate form of a commercial anion exchange resin gave formate esters in good yields. The formates were hydrolysed efficiently to the corresponding alcohols by a brief treatment with hydrochloric acid. Reaction of primary alkyl bromides or iodides, secondary alkyl bromides, cinnamyl and arylmethyl halides in tetrahydropyran or 1,4-dioxane with the bicarbonate form of the same anion-exchange resin gave the corresponding alcohols directly in good yields. This latter reaction can be carried out successfully in the presence of ester or amide groups.
Exclusive 1,2-reduction of functionalised conjugated aldehydes with sodium triacetoxyborohydride
Singh, Jasvinder,Sharma, Munisha,Kaur, Irvinder,Kad, Goverdhan L.
, p. 1515 - 1519 (2000)
Functionalised α,β-unsaturated aldehydes were exclusively reduced to allylic alcohols with sodium-triacetoxyborohydride. Neither saturated alcohol nor saturated aldehydes are obtained. Conjugated ketones are not reduced.
Core-shell AgNP@CeO2 nanocomposite catalyst for highly chemoselective reductions of unsaturated aldehydes
Mitsudome, Takato,Matoba, Motoshi,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 5255 - 5258 (2013)
Selective silver: A core-shell AgNP-CeO2 nanocomposite (AgNP@CeO2) acted as an effective catalyst for the chemoselective reductions of unsaturated aldehydes to unsaturated alcohols with H2 (see figure). Maximizing the AgNP-CeO2 interaction successfully induced the heterolytic cleavage of H2, resulting in highly chemoselective reductions. Furthermore, a highly dispersed AgNP@CeO2 system was also developed that exhibited a higher activity than the original AgNP@CeO2. Copyright
Pinacol coupling of aromatic aldehydes and ketones using TiCl 3-Al-EtOH under ultrasound irradiation
Li, Ji-Tai,Lin, Zhi-Ping,Qi, Na,Li, Tong-Shuang
, p. 4339 - 4348 (2004)
Titanium trichloride in EtOH can be reduced by Al to the corresponding low-valent titanium complexes. This can reduce some aromatic aldehydes and ketones to the corresponding pinacols in 40-82% yields within 30-90 min at r.t. under ultrasound irradiation.
A SIMPLE PROCEDURE FOR THE SYNTHESIS OF THREE-CARBON HOMOLOGATED BORONATE ESTERS AND TERMINAL ALKENES VIA NUCLEOPHILIC DISPLACEMENT IN α-HALOALLYLBORONATE ESTER
Brown, Herbert C.,Rangaishenvi, Milind V.
, p. 7115 - 7118 (1990)
The transfer reactions of α-haloallylboronate ester 1 with representative organolithium and Grignard reagents provide α-alkyl- or α-aryl-substituted allylboronate esters, readily converted into three-carbon homologated boronate esters and terminal alkenes.
Cofactor recycling for selective enzymatic biotransformation of cinnamaldehyde to cinnamyl alcohol
Zucca, Paolo,Littarru, Maria,Rescigno, Antonio,Sanjust, Enrico
, p. 1224 - 1226 (2009)
The enzymatic, selective hydrogenation of cinnamaldehyde to cinnamyl alcohol is reported here. Yeast alcohol dehydrogenase was used in a substrate-coupled process with cofactor recycling. Both 100% selectivity and aldehyde conversion were achieved within
Poly(1,4-butyl-bis-vinylpyridinium) borohydride as a new stable and efficient reducing agent in organic synthesis
Khaligh, Nader Ghaffari
, p. 721 - 727 (2013)
The unstable sodium borohydride is stabilized on modified poly(4-vinylpyridinium), and it is used as an efficient and regenerable polymer-supported borohydride reagent for the reduction of a variety of carbonyl compounds, such as aldehydes, ketones, α,β-unsaturated carbonyl compounds, α-diketones and acyloins, in good to excellent yields.
Quaternized amino functionalized cross-linked polyacrylamide as a new solid - Liquid phase transfer catalyst in reduction of carbonyl compounds with NaBH4
Tamami, Bahman,Mahdavi, Hossein
, p. 821 - 826 (2003)
Poly[N-(2-aminoethyl)acrylamido]trimethyl ammonium chloride resin was developed as a new polymeric phase transfer catalyst. This quaternized polyacrylamide catalyzed the chemoselective reduction of aldehydes and ketones by NaBH4 to give corresponding alcohols in high yields under mild conditions.
Promotion of Sn on the Pd/AC catalyst for the selective hydrogenation of cinnamaldehyde
Zhao, Jia,Xu, Xiaoliang,Li, Xiaonian,Wang, Jianguo
, p. 102 - 106 (2014)
The effect of Sn on the Pd/AC catalysts for the selective hydrogenation of cinnamaldehyde (CALD) was investigated. TEM, EDX, XRD and XPS have been employed to characterize Pd-Sn/AC. 80% cinnamyl alcohol (COL) selectivity can be obtained at 96% CALD conversion, even 100% selectivity can be achieved at 3% conversion. The PdSn type alloy is responsible for the enhancement of unsaturated alcohol (UA) selectivity, as confirmed by XRD and EDX. XPS technique confirmed that the promoting effect of Sn was related to Pd-Sn interaction. The favorable adsorption of C = O bond on the PdSn has been supported by means of density functional theory.
Cationic [2,6-Bis(2′-oxazolinyl)phenyl]palladium(II) Complexes: Catalysts for the Asymmetric Michael Reaction
Stark, Mark A.,Jones, Geraint,Richards, Christopher J.
, p. 1282 - 1291 (2000)
Reaction of 1,3-dicyanobenzene with β-amino alcohols (S)-H2NCHRCH2OH (R = iPr, iBu, tBu, CH2Cy, CH2Ph) and (R)-H2NCHPhCH2OH gave new 1,3-bis(2′-oxazolinyl)benzenes (30-51%). These, together with 1,3-bis(4′,4′-dimethyl-2′-oxazolinyl)benzene, were treated with LDA/TMEDA followed by the addition of PdBr2(1,5-COD) to give [2,6-bis(2′-oxazolinyl)phenyl]-palladium(II) bromide complexes (21-41%). In two cases no complexes were obtained (R = Ph, CH2Ph) due to ring opening of the oxazolines by LDA/TMEDA. Treatment of the palladium complexes with AgBF4, AgOTf, or AgSbF6 in wet CH2Cl2 provided a series of cationic [2,6-bis(2′-oxazolinyl)phenyl]palladium complexes (28-87%) containing water coordinated to palladium, as established by an X-ray crystal structure analysis of (S,S)-[2,6-bis(4′-isopropyl-2′-oxazolinyl)phenyl]aquopalladium(II) trifluoromethanesulfonate. All of the cationic complexes proved to be efficient catalysts for the Michael reaction between α-cyanocarboxylates and methyl vinyl ketone and between acrylonitrile and activated Michael donors. Selectivities of up to 34% ee were obtained for the formation of (R)-ethyl 2-cyano-2-methyl-5-oxohexanoate.
Pyridine: N-oxide promoted hydrosilylation of carbonyl compounds catalyzed by [PSiP]-pincer iron hydrides
Chang, Guoliang,Fenske, Dieter,Fuhr, Olaf,Li, Xiaoyan,Sun, Hongjian,Xie, Shangqing,Yang, Wenjing,Zhang, Peng
, p. 9349 - 9354 (2020)
Five [PSiP]-pincer iron hydrides 1-5, [(2-Ph2PC6H4)2HSiFe(H)(PMe3)2 (1), (2-Ph2PC6H4)2MeSiFe(H)(PMe3)2 (2), (2-Ph2PC6H4)2PhSiFe(H)(PMe3)2 (3), (2-(iPr)2PC6H4)2HSiFe(H)(PMe3) (4), and (2-(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (5)], were used as catalysts to study the effects of pyridine N-oxide and the electronic properties of [PSiP]-ligands on the catalytic hydrosilylation of carbonyl compounds. It was proved for the first time that this catalytic process could be promoted with pyridine N-oxide as the initiator at 30 °C because the addition of pyridine N-oxide is beneficial for the formation of an unsaturated hydrido iron complex, which is the key intermediate in the catalytic mechanism. Complex 4 as the best catalyst shows excellent catalytic performance. Among the five complexes, complex 3 was new and the molecular structure of complex 3 was determined by single crystal X-ray diffraction. A proposed mechanism was discussed.
Hydrogenation of α,β-Unsaturated Aldehydes and Ketones to the Unsaturated Alcohols catalysed by Hydridoiridium Phosphine Complexes
Farnetti, E.,Pesce, M.,Kaspar, J.,Spogliarich, R.,Graziani, M.
, p. 746 - 747 (1986)
Unusual selective hydrogenation of cinnamaldehyde and benzylideneacetone to the corresponding unsaturated alcohols is catalysed by (+) complexes in toluene; use of a chiral phosphine gives a 7.4percent enantiomeric excess of (S)-(-)-1-phenylbut-1-en-3-ol.
Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols
Emayavaramban, Balakumar,Roy, Moumita,Sundararaju, Basker
, p. 3952 - 3955 (2016)
Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product. The iron way! A direct amination of allylic alcohols has been demonstrated without the need of Lewis acid activators using an efficient and regiospecific molecular iron catalyst. A range of amines and alcohols were tolerated, and the reaction was found to procced through an oxidation/reduction (redox) pathway (see scheme).
Polymer Supported Zirconium Borohydride: a Stable, Efficient and Regenerable Reducing Agent
Tamami, Bahman,Goudarzian, Nouredin
, p. 1079 - 1080 (1994)
The unstable zirconium borohydride, Zr(BH4)4, is stabilized on polyvinylpyridine and used as a new, stable, efficient and regenerable polymer supported transition-metal borohydride reagent for reduction of a variety of carbonyl compounds.
Chemoselective transfer hydrogenation of carbonyl compounds catalyzed by macrocyclic nickel (II)complex
Phukan, Prodeep,Sudalai
, p. 2401 - 2405 (2000)
Macrocyclic Ni(II) complex, 1, catalyzes efficiently the chemoselective transfer reduction of carbonyl compounds in presence of propan-2-ol/KOH or HCO2H/HCO2NH4 as hydrogen donors to produce the corresponding alcohols in high yield.
Hydrosilylation of aldehydes and ketones catalyzed by an n-heterocyclic carbene-nickel hydride complex under mild onditions
Bheeter, Linus P.,Henrion, Mickael,Brelot, Lydia,Darcel, Christophe,Chetcuti, Michael J.,Sortais, Jean-Baptiste,Ritleng, Vincent
, p. 2619 - 2624 (2012)
Half-sandwich N-heterocyclic carbene (NHC)-nickel complexes of the general formula [NiACHTUNGTRENUNG(NHC)ClCp?] (Cp?= Cp, Cp*) efficiently catalyze the hydrosilylation of aldehydes and ketones at room temperature in the presence of a catalytic amount of sodium triethylborohydride and thus join the fairly exclusive club of well-defined nickel(II) catalyst precursors for the hydrosilylation of carbonyl functionalities. Of notable interest is the isolation of an intermediate nickel hydride complex that proved to be the real catalyst precursor.
A mild and chemoselective method for the deprotection of tert-butyldimethylsilyl (TBDMS) ethers using iron(III) tosylate as a catalyst
Bothwell, Jason M.,Angeles, Veronica V.,Carolan, James P.,Olson, Margaret E.,Mohan, Ram S.
, p. 1056 - 1058 (2010)
The most common method for the deprotection of TBDMS ethers utilizes stoichiometric amounts of tetrabutylammonium fluoride, n-Bu4N+F- (TBAF), which is highly corrosive and toxic. We have developed a mild and chemoselective method for the deprotection of TBDMS, TES, and TIPS ethers using iron(III) tosylate as a catalyst. Phenolic TBDMS ethers, TBDPS ethers and the BOC group are not affected under these conditions. Iron(III) tosylate is an inexpensive, commercially available, and non-corrosive reagent.
SELECTIVE REDUCTION OF ALDEHYDES BY A FORMIC ACID- TRIALKYLAMINE- RuCl2(PPh3)3 SYSTEM
Khai, Bui The,Arcelli, Antonio
, p. 3365 - 3368 (1985)
In the presence of trialkylamine and formic acid, RuCl2(PPh3)3 selectively reduces aldehydes to the corresponding alkohols at room temperature.Other reducible groups are unaffected.
A mild method for the deprotection of tetrahydropyranyl (THP) ethers catalyzed by iron(III) tosylate
Bockman, Matthew R.,Angeles, Veronica V.,Martino, Julia M.,Vagadia, Purav P.,Mohan, Ram S.
, p. 6939 - 6941 (2011)
A mild method for the deprotection of THP ethers catalyzed by iron(III) tosylate (2.0 mol %) in CH3OH has been developed. Iron(III) tosylate, Fe(OTs)3·6H2O, is a commercially available solid that is inexpensive, noncorrosive, and easy to handle. The room temperature reaction conditions make this method attractive for deprotection of a range of THP ethers.
Caro's acid supported on silica gel. Part V: A mild and selective reagent for conversion of trimethyl silyl ethers to the corresponding hydroxy compounds
Lakouraj,Tajbakhsh,Khojasteh
, p. 1865 - 1870 (2003)
Mild and efficient method for deprotection of silyl ethers to alcohols is described using Caro's acid supported on silica gel. Reactions are carried out in dichloromethane at room temperature and their parent hydroxy compounds obtained in good to excellent yields. Using this procedure, tetrahydropyranyl ethers (THP) remain intact during desilylation reaction.
New heterogeneous B(OEt)3-MCM-41 catalyst for preparation of α,β-unsaturated alcohols
Uysal, Burcu,Oksal, Birsen S.
, p. 3893 - 3911 (2013)
Grafting of boron tri-ethoxide on mesoporous MCM-41 resulted in a highly active catalyst for the Meerwein-Ponndorf-Verley (MPV) reduction and the catalyst denoted as B(OEt)3-MCM-41. Chemoselective reduction of α,β-unsaturated aldehydes and ketones to the corresponding α,β-unsaturated alcohols was achieved by MPV reduction reaction using a new B(OEt)3-MCM-41 catalyst. The prepared new heterogeneous catalyst, B(OEt)3-MCM-41, was characterized in detail by using XRD, 29Si NMR-, 11B NMR-, 13C NMR-, and TEM, N2 adsorption, and ICP-OES. The results demonstrated the successful homogenous distribution of the B(OEt)3 on the MCM-41 support. The heterogeneous B(OEt)3-MCM-41 catalyst, in comparison with the homogeneous B(O i Pr)3 and B(OEt)3 catalysts, displayed similiar catalytic activity in the MPV reduction of α,β-unsaturated aldehydes and ketones with alcohols as reductants. Reduced reaction times and very high selectivities for the unsaturated alcohols were obtained with the heterogenous catalyst compared with the homogeneous catalysts. The B(OEt)3-MCM-41 catalyst was found to be encouraging, as is is recyclable up to six cycles without any significant loss in its catalytic activity.
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Rylander,Steele
, p. 1579 (1969)
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Chemoselective reduction of carbonyl compounds to alcohols with co-doped ammonia borane
Huang, Pengmian,Tang, Wenjuan,Tan, Guishan,Zeng, Wenbin,Li, Yuanjian,Zhang, Qinghua,Chen
, p. 8248 - 8250 (2014)
Chemoselective reduction of various carbonyl compounds to alcohols with Co-doped ammonia borane was investigated in the present work. It was observed that Co-doped ammonia borane exhibited much better performance than ammonia borane. The Co-based catalysts could be reused up to four times with a slight decrease in activity. Thus, a mild and efficient method for chemoselective reduction of carbonyl compounds with Co-doped ammonia borane was established. The Co-doped ammonia borane sample was characterized by electron paramagnetic resonance. Electron paramagnetic resonance characterization revealed that Co element in a partially reduced state.
Low-temperature reduction of bio-based cinnamaldehyde to α,β-(un)saturated alcohols enabled by a waste-derived catalyst
Jian, Yumei,Li, Hu,Luo, Xiaoxiang
, (2022/01/06)
A waste eggshell-derived catalyst (CaO-900) was facilely prepared and exhibited high efficiency in selective hydrogenation of bio-based cinnamaldehyde (CAL) to cinnamyl alcohol (COL) with 97% yield at 30 °C. By simply adjusting reaction temperature and time, CAL could be completely converted to 3-phenylpropanol. The predominant catalytic performance of CaO-900 could be attributed to its high alkalinity and large specific surface area. In situ Raman and theoretical calculations indicated that the priority of hydrosilylation toward CAL played a crucial role in the control of product distribution. In addition, the CaO-900 catalyst showed good recyclability.
Platinum supported on nanosilica and fibrous nanosilica for hydrogenation reactions
Erasmus, E.,Xantini, Z.
, (2020/11/24)
Platinum nanoparticles supported on nanosilica (NP) and fibrous nanosilica (dendritic fibrous nano-spheres, DFNS) were prepared by direct grafting of the Pt precursor onto the silanol groups or via a polyethylenimine (PEI) linker. From the SEM and TEM images the average diameter of the nanosilica and fibrous nanosilica (DFNS), was determined to be 21.4 and 503 nm, respectively. While surface areas as measured by ASAP is 463.4 m2 g?1 for DFNS and 142.5 m2 g?1 for the nanosilica. For the four Pt containing catalysts (Pt/NP, Pt/DFNS, Pt/PEI/NP and Pt/PEI/DFNS), a Pt loading between 1.35 × 1017 and 8.46 × 1017 Pt atoms per gram support were determined. The PEI-containing catalyst gave higher Pt-loading than the direct anchoring of the Pt onto the silanol groups of the support. The catalysts were further characterised ATR FTIR and XPS. After oxidation of the pre-catalysts 85% of the Pt was in the oxide form. While after reduction, ca. 82% the Pt supported on DFNS was in the metallic form. Reduction of the Pt supported on NP, resulted in 100% of the Pt in the Pt0 oxidation state. These catalysts were tested for the hydrogenation of C[dbnd]C and/or C[dbnd]O bonds in cyclohexene, benzaldehyde and cinnamaldehyde. The % conversion and product distribution will be discussed in term of diameter, surface area and Pt-loading.
Direct Heterogenization of the Ru-Macho Catalyst for the Chemoselective Hydrogenation of α,β-Unsaturated Carbonyl Compounds
Padmanaban, Sudakar,Gunasekar, Gunniya Hariyanandam,Yoon, Sungho
supporting information, p. 6881 - 6888 (2021/03/01)
In this study, a commercially available homogeneous pincer-type complex, Ru-Macho, was directly heterogenized via the Lewis acid-catalyzed Friedel-Crafts reaction using dichloromethane as the cross-linker to obtain a heterogeneous, pincer-type Ru porous organometallic polymer (Ru-Macho-POMP) with a high surface area. Notably, Ru-Macho-POMP was demonstrated to be an efficient heterogeneous catalyst for the chemoselective hydrogenation of α,β-unsaturated carbonyl compounds to their corresponding allylic alcohols using cinnamaldehyde as a model compound. The Ru-Macho-POMP catalyst showed a high turnover frequency (TOF = 920 h-1) and a high turnover number (TON = 2750), with high chemoselectivity (99%) and recyclability during the selective hydrogenation of α,β-unsaturated carbonyl compounds.