- Stereospecific Intramolecular Reductive Cross-Electrophile Coupling Reactions for Cyclopropane Synthesis
-
The stereospecific reductive cross-electrophile coupling reaction of 2-aryl-4-chlorotetrahydropyrans to afford disubstituted cyclopropanes is reported. This ring contraction presents surprises with respect to the stereochemical outcome of reaction of the
- Tollefson, Emily J.,Erickson, Lucas W.,Jarvo, Elizabeth R.
-
-
Read Online
- Copper(i) and silver(i) chemistry of vinyltrifluoroborate supported by a bis(pyrazolyl)methane ligand
-
Although unsaturated organotrifluoroborates are common synthons in metal-organic chemistry, their transition metal complexes have received little attention. [CH2(3,5-(CH3)2Pz)2]Cu(CH2CHBF3), (SIPr)Cu(MeCN)(CH2CHBF3) and [CH2(3,5-(CH3)2Pz)2]Ag(CH2CHBF3) represent rare, isolable molecules featuring a vinyltrifluoroborate ligand on coinage metals. The X-ray crystal structures show the presence of three-coordinate metal sites in these complexes. The vinyltrifluoroborate group binds asymmetrically to the metal site in [CH2(3,5-(CH3)2Pz)2]M(CH2CHBF3) (M = Cu, Ag) with relatively closer M-C(H)2distances. The computed structures of [CH2(3,5-(CH3)2Pz)2]M(CH2CHBF3) and M(CH2CHBF3), however, have shorter M-C(H)BF3distances than M-C(H)2. These molecules feature various inter- or intra-molecular contacts involving fluorine of the BF3group, possibly affecting these M-C distances. The binding energies of [CH2CHBF3]?to Cu+, Ag+and Au+have been calculated at the wB97XD/def2-TZVP level of theory, in the presence and absence of the supporting ligand CH2(3,5-(CH3)2Pz)2. The calculation shows that Au+has the strongest binding to the [CH2CHBF3]?ligand, followed by Cu+and Ag+, irrespective of the presence of the supporting ligand. However, in all three metals, the supporting ligand weakens the binding of olefin to the metal. The same trends were also found from the analysis of the σ-donation and π-backbonding interactions between the metal fragment and the π and π* orbitals of [CH2CHBF3]?
- Dias, H. V. R.,Mao, James X.,Nam, Kwangho,Zacharias, Adway O.
-
-
Read Online
- Triphosgene-pyridine mediated stereoselective chlorination of acyclic aliphatic 1,3-diols
-
We describe a strategy to chlorinate stereocomplementary acyclic aliphatic 1,3-diols using a mixture of triphosgene and pyridine. While 1,3-anti diols readily led to 1,3-anti dichlorides, 1,3-syn diols must be converted to 1,3-syn diol monosilylethers to access the corresponding 1,3-syn dichlorides. These dichlorination protocols were operationally simple, very mild, and readily tolerated by advanced synthetic intermediates.
- Villalpando, Andrés,Saputra, Mirza A.,Tugwell, Thomas H.,Kartika, Rendy
-
-
Read Online
- Visible Light-Promoted Recyclable Carbon Nitride-Catalyzed Dioxygenation of β,γ-Unsaturated Oximes
-
A visible-light-induced dioxygenation of β,γ-unsaturated oximes for the synthesis of diverse useful isoxazolines bearing a hydroxyl moiety was developed by employing graphitic carbon nitride (g-C3N4) as a heterogeneous photocatalyst under an air atmosphere. Noted that, the eminent advantages of this metal-free protocol include step economy, easy operation, a recyclable photocatalyst, external reductant-/oxidant-free and mild reaction conditions. Additionally, mechanistic studies indicated hydroxyl radical was generated under the photocatalysis of g-C3N4.
- Fu, Xiao-Yang,Si, Ya-Feng,Qiao, Li-Peng,Zhao, Yu-Fen,Chen, Xiao-Lan,Yu, Bing
-
supporting information
p. 574 - 580
(2021/11/13)
-
- Allylation and propargylation of aldehydes mediated byin situgenerated zinc from the redox couple of Al and ZnCl2in 2N HCl
-
A simple one pot allylation and propargylation of aldehydes mediated by zinc(0), which isin situgenerated from the redox couple of Al and ZnCl2in 2N HCl, is demonstrated to afford the corresponding homoallyl and homopropargyl alcohols with exce
- Mondal, Bibhas,Adhikari, Utpal,Hajra, Partha Pratim,Roy, Ujjal Kanti
-
p. 7163 - 7173
(2021/05/03)
-
- Photoredox Allylation Reactions Mediated by Bismuth in Aqueous Conditions
-
Organometallic allylic reagents are widely used in the construction of C?C bonds by Barbier-type reactions. In this communication, we have described a photoredox Barbier allylation of aldehydes mediated by bismuth, in absence of other metals as co-reductants. Mild reaction conditions, tolerance of oxygen, and use of aqueous solvent make this photoredox methodology attractive for green and sustainable synthesis of homoallylic alcohols.
- Potenti, Simone,Gualandi, Andrea,Puggioli, Alessio,Fermi, Andrea,Bergamini, Giacomo,Cozzi, Pier Giorgio
-
supporting information
p. 1624 - 1627
(2021/02/05)
-
- Ni-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems
-
A nickel-catalyzed 1,2-diarylation of alkenyl ketones with aryl iodides and arylboronic esters is reported. Ketones with a variety of substituents serve as effective directing groups, offering high levels of regiocontrol. A representative product is diversified into a wide range of useful products that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis reveals the effect of electronic factors on initial rates.
- Apolinar, Omar,Derosa, Joseph,Engle, Keary M.,Karunananda, Malkanthi K.,Kleinmans, Roman,Li, Zi-Qi,Tran, Van T.,Wisniewski, Steven R.
-
supporting information
p. 5311 - 5316
(2021/07/26)
-
- Nickel-Catalyzed Reductive Allylation of Aldehydes with Allyl Acetates
-
Carbonyl allylation reactions constitute an important step in the formation of carbon-carbon reactions, and involve various related reactions that chiefly use allylmetal reagents. This report presents a nickel-catalyzed carbonyl allylation reaction using allyl acetate, which produces homoallyl alcohols in moderate to good yields, as an efficient methodology under reductive coupling conditions.
- Suzuki, Hiroyuki,Yamaguchi,Itoh, Akichika
-
p. 1489 - 1494
(2020/12/13)
-
- Enantiomerically Enriched α-Borylzinc Reagents by Nickel-Catalyzed Carbozincation of Vinylboronic Esters
-
In this paper is described a synthesis of enantiomerically enriched, configurationally stable organozinc reagents by catalytic enantioselective carbozincation of a vinylboronic ester. This process furnishes enantiomerically enriched α-borylzinc intermediates that are shown to undergo stereospecific reactions, producing enantioenriched secondary boronic ester products. The properties of the intermediate α-borylzinc reagent are probed and the synthetic utility of the products is demonstrated by application to the synthesis of (-)-aphanorphine and (-)-enterolactone.
- Chen, Jingjia,Hu, Weipeng,Jin, Jing,Lovinger, Gabriel J.,Morken, James P.,Zhang, Chenlong
-
supporting information
p. 14189 - 14195
(2021/09/11)
-
- Indium(I)/CuFe2O4 Reagent for Allylation of Carbonyls and Epoxide Rearranged Carbonyls
-
Abstract: Indium(I)/CuFe2O4 reagent forcarbonyl allylation and epoxide rearranged carbonyl allylation is proposed forformation of homoallylic alcohols. The In(I) reagent in combination withcatalytic amount of CuFe2O4support in situ formation of nucleophilicallylic indium from allyl halide in THF medium. Nucleophilic allylic indiumspecies react with carbonyls to form homoallyl alcohols in good to excellentyields. Under the presented reaction conditions arylepoxides undergo smoothrearrangement into aldehydes that are also allylated with formation of homoallylalcohols. The process is highly efficient and tolerates different functionalgroups.
- Kundu, M.,Mandal, S. P.,Mondal, B.,Roy, U. K.
-
p. 2189 - 2196
(2020/12/25)
-
- A Mechanochemical Zinc-Mediated Barbier-Type Allylation Reaction under Ball-Milling Conditions
-
A ball-milling-enabled zinc-mediated Barbier-type allylation reaction is reported. Notably, running the reaction in this manner renders it effective irrespective of the initial morphology of the zinc metal. The process is operationally simple, does not re
- Yin, JieXiang,Stark, Roderick T.,Fallis, Ian A.,Browne, Duncan L.
-
p. 2347 - 2354
(2020/02/04)
-
- Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water
-
Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].
- Sawkmie, Micky Lanster,Paul, Dipankar,Khatua, Snehadrinarayan,Chatterjee, Paresh Nath
-
-
- Synthesis of Enantiomerically Pure 5,6-Dihydropyran-2-ones via Chemoenzymatic Sequential DKR-RCM Reaction
-
The enantiomerically pure 5,6-dihydropyran-2-ones play a crucial role as the building blocks in the synthesis of various bioactive compounds. A new straightforward protocol toward enantiomerically pure 5,6-dihydropyran-2-ones based on enzymatic dynamic ki
- Koszelewski, Dominik,Borys, Filip,Brodzka, Anna,Ostaszewski, Ryszard
-
supporting information
p. 1653 - 1658
(2019/01/24)
-
- An alternative synthesis of the CNS stimulant Prolintane
-
An alternative synthesis of prolintane, a CNS stimulant, is reported using commercially available allylbenzene in good overall yield (32.3%). The key transformations include epoxidation, Grignard reaction, Mitsunobu and reduction protocols.
- Mujahid,Korpe,Deshmukh,Bhadange,Muthukrishnan
-
-
- Cationic Cobalt Porphyrin-Catalyzed Allylation of Aldehydes with Allyltrimethylsilanes
-
Cationic cobalt porphyrin-catalyzed allylation of aldehydes with allyltrimethylsilanes is developed. The formation of the aldehyde-cobalt porphyrin complex, the key intermediate for the addition of allylsilanes, is confirmed by theoretical studies and syn
- Tomifuji, Rei,Masuda, Shota,Kurahashi, Takuya,Matsubara, Seijiro
-
supporting information
p. 3834 - 3837
(2019/05/24)
-
- Exploring the Sponge Consortium Plakortis symbiotica-Xestospongia deweerdtae as a Potential Source of Antimicrobial Compounds and Probing the Pharmacophore for Antituberculosis Activity of Smenothiazole A by Diverted Total Synthesis
-
Fractionation of the bioactive CHCl3-MeOH (1:1) extracts obtained from two collections of the sponge consortium Plakortis symbiotica-Xestospongia deweerdtae from Puerto Rico provided two new plakinidone analogues, designated as plakinidone B (2) and plakinidone C (3), as well as the known plakinidone (1), plakortolide F (4), and smenothiazole A (5). The structures of 1-5 were characterized on the basis of 1D and 2D NMR spectroscopic, IR, UV, and HRMS analysis. The absolute configurations of plakinidones 2 and 3 were established through chemical correlation methods, VCD/ECD experiments, and spectroscopic data comparisons. When assayed in vitro against Mycobacterium tuberculosis H37Rv, none of the plakinidones 1-3 displayed significant activity, whereas smenothiazole A (5) was the most active compound, exhibiting an MIC value of 4.1 μg/mL. Synthesis and subsequent biological screening of 8, a dechlorinated version of smenothiazole A, revealed that the chlorine atom in 5 is indispensable for anti-TB activity.
- Jiménez-Romero, Carlos,Rode, Joanna E.,Pérez, Yeiry M.,Franzblau, Scott G.,Rodríguez, Abimael D.
-
p. 2295 - 2303
(2017/09/01)
-
- Tert-Butyl Nitrite: Organic Redox Cocatalyst for Aerobic Aldehyde-Selective Wacker-Tsuji Oxidation
-
An aldehyde-selective aerobic Wacker-Tsuji oxidation is developed. Using tert-butyl nitrite as a simple organic redox cocatalyst instead of copper or silver salts, a variety of aldehydes were achieved as major products in up to 30/1 regioselectivity as well as good to high yields at room temperature.
- Ning, Xiao-Shan,Wang, Mei-Mei,Yao, Chuan-Zhi,Chen, Xian-Min,Kang, Yan-Biao
-
supporting information
p. 2700 - 2703
(2016/06/15)
-
- Mild bottom-up synthesis of indium(0) nanoparticles: Characterization and application in the allylation of carbonyl compounds
-
Very reactive, monodisperse (4.0 ± 0.5 nm) spherical indium(0) nanoparticles have been generated in situ, in a simple, mild and efficient way, by fast reduction of commercially available indium(iii) chloride with lithium sand and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB) in THF, at room temperature, and in the absence of any anti-agglomeration additives or ligands. The as-synthesized bare InNPs were applied for the allylation of a variety of aldehydes and ketones. For most of the compounds tested, the corresponding homoallylic alcohols were obtained as the major product in good to excellent yield.
- Dorn, Viviana,Chopa, Alicia,Radivoy, Gabriel
-
p. 23798 - 23803
(2016/03/12)
-
- Selective access to all four diastereomers of a 1,3-amino alcohol by combination of a keto reductase- and an amine transaminase-catalysed reaction
-
The biocatalytic synthesis of chiral amines has become a valuable addition to the chemists' toolbox. However, the efficient asymmetric synthesis of functionalised amines bearing more than one stereocentre, such as 1,3-amino alcohols, remains challenging. By employing a keto reductase (KRED) and two enantiocomplementary amine transaminases (ATA), we developed a biocatalytic route towards all four diastereomers of 4-amino-1-phenylpentane-2-ol as a representative molecule bearing the 1,3-amino alcohol functionality. Starting from a racemic hydroxy ketone, a kinetic resolution using an (S)-selective KRED provided optically active hydroxy ketone (86% ee) and the corresponding diketone. Further transamination of the hydroxy ketone was performed by either an (R)- or an (S)-selective ATA, yielding the (2R,4R)- and (2R,4S)-1,3-amino alcohol diastereomers. The remaining two diastereomers were accessible in two subsequent asymmetric steps: the diketone was reduced regio- and enantioselectively by the same KRED, which yielded the (S)-configured hydroxy ketone. Eventually, the subsequent transamination of the crude product with (R)- and (S)-selective ATAs yielded the remaining (2S,4R)- and (2S,4S)-diastereomers, respectively.
- Kohls, Hannes,Anderson, Mattias,Dickerhoff, Jonathan,Weisz, Klaus,C?rdova, Armando,Berglund, Per,Brundiek, Henrike,Bornscheuer, Uwe T.,H?hne, Matthias
-
supporting information
p. 1808 - 1814
(2015/06/02)
-
- Oxime-mediated oxychlorination and oxybromination of unactivated olefins
-
An oxime-mediated oxychlorination and oxybromination of unactivated olefins relying on palladium catalysis has been developed. A wide range of chlorinated and brominated isoxazolines has been synthesized in moderate to good yields. To demonstrate the value of the method, the brominated isoxazoline has been further converted to other useful synthetic feedstock.
- Dong, Kui-Yong,Qin, Hai-Tao,Liu, Feng,Zhu, Chen
-
supporting information
p. 1419 - 1422
(2015/03/04)
-
- Hydroxyl-directed stereoselective diboration of alkenes
-
An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.
- Blaisdell, Thomas P.,Caya, Thomas C.,Zhang, Liang,Sanz-Marco, Amparo,Morken, James P.
-
supporting information
p. 9264 - 9267
(2014/07/21)
-
- One-pot sequential 1,4- and 1,2-reductions of α,β-unsaturated δ-lactones to the corresponding δ-lactols with CuCl and NaBH 4 in methanol
-
An efficient, one-pot method for the highly chemoselective synthesis of δ-lactols from α,β-unsaturated δ-lactones using CuCl and NaBH4 in methanol was developed. Georg Thieme Verlag Stuttgart. New York.
- Matsumoto, Yasunobu,Yonaga, Masahiro
-
supporting information
p. 1764 - 1768
(2014/08/05)
-
- Oxime-mediated facile access to 5-methylisoxazoles and applications in the synthesis of valdecoxib and oxacillin
-
A palladium-catalyzed efficient synthesis of 5-methylisoxazoles via oxime-mediated functionalization of unactivated olefins is described. The reaction affords a variety of 5-methylisoxazoles in moderate to good yields. To further demonstrate the utility of the method, the rapid synthesis of valdecoxib and oxacillin is reported. (Chemical Equation Presented).
- Dong, Kui-Yong,Qin, Hai-Tao,Bao, Xing-Xing,Liu, Feng,Zhu, Chen
-
supporting information
p. 5266 - 5268
(2015/01/09)
-
- Dynamic kinetic resolution of homoallylic alcohols: Application to the synthesis of enantiomerically pure 5,6-dihydropyran-2-ones and δ-lactones
-
Dynamic kinetic resolution of various homoallylic alcohols with the use of Candida antarctica lipase B and ruthenium catalyst 2 afforded homoallylic acetates in high yields and with high enantioselectivity. These enantiopure acetates were further transfor
- Warner, Madeleine C.,Shevchenko, Grigory A.,Jouda, Suzan,Bogar, Krisztian,Baeckvall, Jan-E.
-
supporting information
p. 13859 - 13864
(2013/10/22)
-
- Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones
-
Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.
- Zhuo, Lian-Gang,Yao, Zhong-Ke,Yu, Zhi-Xiang
-
supporting information
p. 4634 - 4637
(2013/10/08)
-
- Nitroalkenes as carbonyl surrogates in arylmethyl-homoallylic alcohol forming one-pot allylation reactions in water
-
A simple and practical approach has been developed for conducting direct, homoallylic alcohol forming allylation reactions of nitroalkenes in water. Employing the new method, various arylmethyl-homoallylic alcohols can be produced from the corresponding, readily prepared β-nitrostyrenes.
- Lin, Mei-Huey,Lin, Wei-Cheng,Liu, Han-Jun,Chuang, Tsung-Hsun
-
p. 1278 - 1282
(2013/03/28)
-
- Rapid synthesis of homoallylic alcohol from aldehyde with allyltributylstannane under solvent-free conditions
-
A catalytic amount (2 mol %) of phosphotungstic acid (PTA) is sufficient to synthesize homoallylic alcohol in excellent yields from aldehyde with allyltributylstannane upon grinding under solvent-free reaction conditions. Easy handling, very short reactio
- Bora, Pranjal P.,Sema, H. Atoholi,Wahlang, Barisha,Bez, Ghanashyam
-
experimental part
p. 167 - 172
(2012/03/07)
-
- 6-Deoxyerythronolide B synthase thioesterase-catalyzed macrocyclization is highly stereoselective
-
Macrocyclic polyketide natural products are an indispensable source of therapeutic agents. The final stage of their biosynthesis, macrocyclization, is catalyzed regio- and stereoselectively by a thioesterase. A panel of substrates were synthesized to test their specificity for macrocyclization by the erythromycin polyketide synthase TE (DEBS TE) in vitro. It was shown that DEBS TE is highly stereospecific, successfully macrocyclizing a 14-member ring substrate with an R configured O-nucleophile, and highly regioselective, generating exclusively the 14-member lactone over the 12-member lactone.
- Pinto, Atahualpa,Wang, Meng,Horsman, Mark,Boddy, Christopher N.
-
supporting information; experimental part
p. 2278 - 2281
(2012/07/03)
-
- NOVEL COMPOUNDS FOR MODULATION OF ORPHAN NUCLEAR RECEPTOR RAR-RELATED ORPHAN RECEPTOR-GAMMA (RORγ GAMMA, NR1F3) ACTIVITY AND FOR THE TREATMENT OF CHRONIC INFLAMMATORY AND AUTOIMMUNE DISEASE
-
The invention provides modulators for the orphan nuclear receptor RORγ and methods for treating RORγ mediated diseases by administrating these novel RORγ modulators to a human or a mammal in need thereof. Specifically, the present invention provides compounds of Formula (1) and the enantiomers, diastereomers, tautomers, solvates and pharmaceutically acceptable salts thereof.
- -
-
Page/Page column 65
(2011/10/03)
-
- Tin mediated allylation reactions of enol ethers in water
-
Under tin-mediated Barbier-type reaction conditions, hydration of enol ethers takes place to form aldehydes that undergo allylation reactions. By using this process, various homoallylic alcohols and 2-halohomoallylic alcohols are produced in good to excel
- Lin, Mei-Huey,Hung, Shiang-Fu,Lin, Long-Zhi,Tsai, Wen-Shing,Chuang, Tsung-Hsun
-
supporting information; experimental part
p. 332 - 335
(2011/03/23)
-
- Aqueous electrosynthesis of carbonyl compounds and the corresponding homoallylic alcohols in a divided cell
-
An aqueous paired electrosynthesis is studied in a divided cell. On graphite anode Br- was oxidized to Br2 and this generated Br2 oxidized alcohols to the corresponding carbonyl compounds while Sn2+ was reduced
- Zhang, Li,Zha, Zhenggen,Wang, Zhiyong,Fu, Shengquan
-
scheme or table
p. 1426 - 1429
(2010/04/29)
-
- An efficient electrochemical method for the paired synthesis of carbonyl compounds and homoallylic alcohols in a simple home-made cell
-
An efficient electrochemical synthesis of carbonyl compounds and homoallylic alcohols was developed in excellent yields using a simple home-made cell. The catalytic redox behavior of the electrode surface and the reaction mechanism was investigated by cyc
- Zhang, Li,Zha, Zhenggen,Wang, Zhiyong
-
supporting information; experimental part
p. 1915 - 1918
(2010/10/18)
-
- Air-stable hypervalent organobismuth(III) tetrafluoroborate as effective and reusable catalyst for the allylation of aldehyde with tetraallyltin
-
Air-stable hypervalent organobismuth(III) tetrafluoroborate (C6H11N(CH2C6H4)2BiBF4) was synthesized and characterized by spectroscopic and X-ray crystallographic techniques. The
- Zhang, Xiaowen,Qiu, Renhua,Tan, Nianyuan,Yin, Shuangfeng,Xia, Jun,Luo, Shenglian,Au, Chak-Tong
-
experimental part
p. 153 - 156
(2010/03/04)
-
- The catalyzed desulfinylative allylation of carbonyl compounds with alk-2-enesulfonyl chlorides and silyl alk-2-enesulfinates
-
Coupling up with sulfonyl chlorides: An ene reaction of alkenes with SO2·BCl3 permits the one-pot conversion of simple alkenes into b,g-unsaturated sulfonyl chlorides or sulfinic silyl esters. These compounds can then be used as nucleophilic allylating agents with aldehydes and ketones to generate the corresponding homoallylic alcohols (see scheme) with good chemo-and diastereoselectivity in the presence of a suitable catalyst and reducing agent.
- Volla, Chandra M. R.,Markovic, Dean,Laclef, Sylvain,Vogel, Pierre
-
scheme or table
p. 8984 - 8988
(2010/10/02)
-
- Indium triiodide catalyzed direct hydroallylation of esters
-
The InI3-catalyzed hydroallylation of esters by using hydroand allysilanes under mild conditions has been accomplished. Many significant groups such as alkenyl, alkynyl, cyano, and nitro ones survive under these conditions. This reaction system, provided routes to both homoallylic alcohols and ethers, in which either elimination of the alkoxy moiety or of the carbonyl oxygen atom could be freely selected by changing the substituents on the alkoxy moiety and on the hydrosilane. In addition, the hydroallylation of lactones took place without ring cleavage to produce the desired cyclic ethers in high yields.
- Nishimoto, Yoshihiro,Inamoto, Yoshihiro,Saito, Takahiro,Yasuda, Makoto,Baba, Akio
-
supporting information; experimental part
p. 3382 - 3386
(2010/08/19)
-
- Allylcopper intermediates with N-heterocyclic carbene ligands: Synthesis, structure, and catalysis
-
(Figure presented) Allylcopper Intermediates with N-heterocyclic carbene liganda are synthesized by transmetalation of allylsiloxane reagents, and the crystal structures of allylcopper compounds are reported. The allylcopper transmetalation is utilized fo
- Russo, Vlncenzo,Herron, Jessica R.,Ball, Zachary T.
-
supporting information; experimental part
p. 220 - 223
(2010/03/30)
-
- Allyltin tribromide: A versatile reagent involved in the ring-opening of epoxides
-
This paper presents a versatile reagent for epoxide cleavage. The allyltin tribromide could act as a novel and easily prepared allylation reagent and halide atom donor to convert epoxides to the corresponding homoallyl alcohols and halohydrins in high yields with excellent regioselectivities under mild reaction conditions, respectively. It could also act as a Lewis acid to catalyze the ring opening reactions of epoxides with alcohols.
- Chen, Guohong,Wang, Xin,Jin, Xiaoqian,Liu, Lingyan,Chang, Weixing,Li, Jing
-
experimental part
p. 1294 - 1301
(2010/11/05)
-
- An electrochemical tandem reaction: One-pot synthesis of homoallylic alcohols from alcohols in aqueous media
-
A tandem electrosynthesis of homoallylic alcohols from alcohols in one-pot was realized. In virtue of this one-pot electrosynthesis, the traditional reaction substrates of allylation were broadened from carbonyl compounds to alcohols.
- Zhang, Li,Zha, Zhenggen,Zhang, Zhenlei,Li, Yunfeng,Wang, Zhiyong
-
supporting information; experimental part
p. 7196 - 7198
(2010/11/04)
-
- The solvent-free addition reaction of allylzinc bromide and carbony compounds
-
The reactivity of organozincs could be enhanced dramatically under solvent-free conditions. Allylzinc bromide can react rapidly with aldehydes and ketones to give homoallylic alcohols in high yields in the absence of a catalyst under sol vent-free conditions in an open atmosphere at room temperature. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Zhang, Yumei,Jia, Xuefeng,Wang, Jin-Xian
-
experimental part
p. 2983 - 2986
(2009/11/30)
-
- Chemoenzymatic asymmetric synthesis of harzia lactone A stereomers
-
A facile chemoenzymatic synthesis of the harzia lactone A enantiomers was developed. A lipase-catalyzed acylation and an enantio-controlled substrate and reagent-controlled Sharpless' asymmetric dihydroxylation are the key features of the synthesis.
- Kumar, Abha N.,Bhatt, Suchitra,Chattopadhyay, Subrata
-
experimental part
p. 205 - 209
(2009/06/06)
-
- Lanthanum trichloride: A simple and efficient catalyst for allylation of aldehydes with allyltributylstannane
-
Aldehydes undergo smooth nucleophilic addition with allyltributyl-stannane in the presence of lanthanum trichloride to afford the corresponding homoallylic alcohols in excellent yields. All the reaction conditions were carried out in acetonitrile solvent at room temperature. In all the cases, the catalyst was used in a catalytic amount (10% mol). Copyright Taylor & Francis Group, LLC.
- Reddy, G. S. Satyanarayana,Sammaiah,Sharada
-
experimental part
p. 3905 - 3911
(2009/12/25)
-
- Magnesium-cadmium chloride, a bimetallic catalyst system for the allylation of aldehydes with allyl bromide: An efficient protocol for the synthesis of homoallylic alcohols
-
A simple and efficient procedure for the allylation of aldehydes has been developed using the magnesium-cadmium chloride reagent system. This bimetallic catalytic system works well in a tetrahydrofuran-water solvent medium. A variety of aldehydes undergo smooth nucleophilic addition with allyl bromide to afford the corresponding homoallylic alcohols in excellent yields. All the reactions were performed at room temperature. Georg Thieme Verlag Stuttgart.
- Venkat Narsaiah,Ramesh Reddy,Gopala Rao,Vijay Kumar,Prakasham,Subba Reddy, Basi V.,Yadav, Jhillu S.
-
experimental part
p. 3461 - 3464
(2009/05/26)
-
- A novel palladium-catalyzed hydroalkoxylation of alkenes with a migration of double bond
-
A novel palladium-catalyzed addition of alcohols to olefins was developed, in which a migration of double bond was involved. By this new method, a variety of allylic ethers were prepared with moderate to high yields under mild conditions. The Royal Society of Chemistry.
- Tan, Jiajing,Zhang, Zuhui,Wang, Zhiyong
-
experimental part
p. 1344 - 1348
(2008/10/09)
-
- Bismuth triflate catalyzed allylation of aldehydes with allylstannane under microwave assistance
-
In the presence of a catalytic amount of bismuth triflate and under microwave irradiation, mixtures of aldehyde and allyl-stannane afforded smoothly the corresponding homoallylic alcohol. A wide variety of aldehydes were treated under these conditions. The reactions proceeded rapidly and afforded smoothly the corresponding homoallylic alcohol in good to very good yields using catalytic amounts of Bi(OTf)3·4H2O (0.5mol-%) and under microwave irradiation for a short time. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Ollevier, Thierry,Li, Zhiya
-
p. 5665 - 5668
(2008/09/17)
-
- Synthesis of alkyl-substituted six-membered lactones through ring-closing metathesis of homoallyl acrylates. An easy route to pyran-2-ones, constituents of tobacco flavor
-
(Chemical Equation Presented) The ring-closing metathesis (RCM) reactions of homoallylic acrylates bearing alkyl substituents on various positions of their skeleton afford the corresponding pentenolides in the presence of carbene ruthenium catalysts. For R3 = R4 = H, or R3 = Me, R4 = H, the reactions are catalyzed by complex [RuCl 2(PCy3)2(=CHPh)], while a second-generation Grubbs catalyst is required when R3 = H and R4 = Me, R3 = R4 = Me, or R3 = i-Pr and R4 = H. Alkyl substitution at the homoallylic carbon (R1, R2) increases the yield of the reaction when both the acrylic and/or homoallylic double bonds are methyl-substituted. The interaction of the catalyst with the substrate in the initiation stage involves the homoallylic double bond rather than the acrylic moiety, and the resulting alkylidene species from the first-generation Grubbs catalyst can be observed by 1H and 31P NMR. The racemic tobacco constituents 4-isopropyl-5,6- dihydropyran-2-one and 4-isopropyltetrahydropyran-2-one are prepared via a short reaction sequence, involving the RCM reaction as the key transformation.
- D'Annibale, Andrea,Ciaralli, Laura,Bassetti, Mauro,Pasquini, Chiara
-
p. 6067 - 6074
(2008/02/10)
-
- Electrophile-induced ether transfer: Stereoselective synthesis of 2,4,6-trisubstituted tetrahydropyrans
-
(Chemical Equation Presented) A negative attack: Synthesis of 4-alkoxy-2,6-cis- and its stereocomplementary 4-alkoxy-2,6-trans- tetrahydropyrans has been achieved in high yield and with excellent stereocontrol by a common strategy: electrophile-induced ether-transfer, cyclization, and functionalization reactions (see scheme; Bn = benzyl; BPS = tert-butyldiphenylsilyl;TBS = tert-butyldimethylsilyl; TEA = triethylamine).
- Kartika, Rendy,Taylor, Richard E.
-
p. 6874 - 6877
(2008/09/19)
-
- The employment of indium nanoparticles in Barbier-type reaction of allylic chloride in water
-
Indium nanoparticles have been employed in the reactions of various carbonyl compounds with allyl (crotyl) chloride in water, affording the corresponding alcohols with high yields. The crotylation gave exclusive γ-adducts with a dominant syn-isomer. Copyr
- Li, Jiaming,Zha, Zhenggen,Sun, Lilin,Zhang, Yan,Wang, Zhiyong
-
p. 498 - 499
(2007/10/03)
-
- Highly efficient water promoted allylation and propargylation of arylepoxides via rearrangement-carbonyl addition
-
A simple and highly efficient one-pot procedure for allylation and propargylation of arylepoxides has been developed. A combination of SnCl 2 and catalytic Pd(0) or Pd(II) promotes the reaction of organic halides and epoxides in DMSO with controlled water addition, leading to the regioselective formation of the corresponding homoallyl and homopropargyl alcohols in good yields.
- Roy, Ujjal Kanti,Roy, Sujit
-
p. 678 - 683
(2007/10/03)
-
- Rapid and solvent-free synthesis of homoallyl or homopropargyl alcohols mediated by zinc powder
-
A rapid and efficient procedure for the solvent-free synthesis of homoallylic and homopropargyl alcohols has been achieved by zinc-mediated Barbier-type reaction of carbonyl compounds at room temperature. Georg Thieme Verlag Stuttgart.
- Wang, Jin-Xian,Jia, Xuefeng,Meng, Tuanjie,Xin, Li
-
p. 2838 - 2844
(2007/10/03)
-
- Chemoselective allylation of aldehydes using cerium(III) chloride: Simple synthesis of homoallylic alcohols
-
Aldehydes undergo smooth nucleophilic addition with allyltributylstannane in the presence of CeCl3·7H2O in acetonitrile under extremely mild reaction conditions to afford the corresponding homoallylic alcohols in excellent yields wit
- Yadav,Reddy,Kondaji,Shyam Sunder Reddy
-
p. 879 - 882
(2007/10/03)
-