Reduction of Aromatic and Aliphatic Esters Using the Reducing Systems MoO2(acac)2 or V(O)(OiPr)3 in Combination with 1,1,3,3‐Tetramethyldisiloxane

Pehlivan, Leyla; Métay, Estelle; Laval, S.; Dayoub, Wissam; Delbrayelle, Dominique; Mignani, Gérard; Lemaire, Marc

doi:10.1002/ejoc.201101016

Cited by 44 publications

(14 citation statements)

References 51 publications

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“…In this chemistry, after an extensive investigation of a variety of conditions, they employed equimolar TMDS/MoO 2 (acac) 2 or TMDS/V(O)(OiPr) 3 in toluene for 16-24 h with the molybdenum system being preferred. 84 The system of PMHS/V(O)(OiPr) 3 worked well for this reduction as well. The addition of 2 mol % of triphenylphosphine oxide allowed for a reduction of the MoO 2 (acac) 2 charge from 5 to 1 mol % with no loss in yield.…”

Section: Tmds Reduction Of Carboxylic Acidsmentioning

confidence: 96%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

104

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The chemistry of tetramethyldisiloxane (TMDS) is largely composed of the reduction of functional groups with increasing applications for carboncarbon bond formation. This reagent can be a safe alternative to H 2 , LiAlH 4 , and other reactive reagents. Notable are the amide conversion to amines and aldehydes, nitro group reductions, nitrile reductions, hydrogenolysis of arylchlorine bonds, reductive formation of sulfides, reductive etherification, reductive opening of ketals, reductive demethoxylation, and formation of nitriles with homologation. Selectivity can be carried out by the choice of catalysts. This review of recent chemistry will focus on synthetically applied reactions of the recent past. Displayed reactions are chosen to be representative of the referenced work, but are also chosen to illustrate a new viewpoint. Finally, where applicable, the results of competing hydrosilanes are presented to compare to the results obtained with TMDS.

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Section: Tmds Reduction Of Carboxylic Acidsmentioning

confidence: 96%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

104

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“…More recently, we and others reported mild, safe, and efficient reduction procedures by using TMDS12 for the direct conversion of a range of functions such as phosphane oxides,11 nitriles,13 amides,14 nitro,15 esters,16 and ketones17 depending on the nature of the metal catalyst. We have shown that, by using a stoichiometric amount of Ti(O i Pr) 4 , aromatic or aliphatic nitriles could be readily converted into the corresponding primary amines in high yield 13.…”

Section: Resultsmentioning

confidence: 99%

An Improved and Safer Synthesis of (R)‐ and (S)‐4,4′‐Diaminomethyl‐BINAP

et al. 2012

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(R)‐ and (S)‐4,4′‐diaminomethyl‐BINAP were prepared in three steps from enantiomerically pure BINAPO in a global yield of 52 %. A regioselective bromination of BINAPO with NBS in HMimPF6 gave the desired 4,4′‐dibromo‐BINAPO in quantitative yield, and the recyclability of the ionic liquid was demonstrated. Copper cyanide cyanation of 4,4′‐dibromo‐BINAPO gave the 4,4′‐dicyano‐BINAPO in 70 % yield. Both enantiomers were characterized by NMR spectroscopy and HPLC analysis, and the structures were confirmed by X‐ray crystallography. The cyano and phosphane oxide groups of the resulting 4,4′‐dicyano‐BINAPO were reduced in one step to the corresponding 4,4′‐diaminomethyl‐BINAP by using tetramethyldisiloxane/Ti(OiPr)4 in 75 % yield.

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“…This is the case of the reduction of fatty acids using the mild reducing agent tetramethyldisiloxane (TMDS) and a catalytic amount of InBr 3 , leading to yields of 90% (Scheme 3). 39 Other authors used TMDS in 3 ] as catalysts, achieving quantitative conversions, 40 and, in another example, the system Cu(OTf) 2 /TMDS yields quantitative amounts of saturated fatty alcohols from the corresponding fatty acids. 41…”

Section: Reduction To Alcohols Ethers and Aldehydesmentioning

confidence: 99%

Synthetic Transformations for the Valorization of Fatty Acid Derivatives

et al. 2017

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Oleochemistry is a growing field from the industrial point of view, and one of the basis for a more sustainable chemical production, less dependent of fossil sources. From this point of view, the development of selective and efficient synthetic transformations of triglycerides and fatty acids and esters is an active research field. This short review describes an overview of the most recent advances in the synthetic transformations of fatty acid derivatives into valuable chemicals. 1 Introduction 2 Triglycerides 2.1 Reactions on the ester group and multistep processes 2.2 Epoxidation 2.3 Ozonolysis 2.4 Cross metathesis 3 Reactions on the ester group of fatty acids and esters 3.1 Synthesis of free carboxylic acids 3.2 Synthesis of carboxylic esters 3.3 Reduction to alcohols and aldehydes 3.4 Synthesis of nitrogenated derivatives 4 Oxidation of Unsaturated Fatty acids and esters 4.1 Epoxidation and reactions of epoxides 4.2 Allylic oxidation 4.3 Synthesis of ketoderivatives 4.4 Oxidative cleavage 5 Addition reactions of unsaturated fatty acids and esters 5.1 Hydrogenation and hydroformilation 5.2 Cycloadditions and related reactions 5.3 Addition of carboxylic acids 5.4 Hydroalkylation 5.5 Radical additions 6 Other reactions of unsaturated fatty acids and esters 6.1 Cross metathesis 6.2 Isomerization 7 Conclusion and outlook

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Reduction of Aromatic and Aliphatic Esters Using the Reducing Systems MoO₂(acac)₂ or V(O)(OiPr)₃ in Combination with 1,1,3,3‐Tetramethyldisiloxane

Abstract: An efficient reduction of aromatic and aliphatic esters with 1,1,3,3-tetramethyldisiloxane in combination with [MoO 2 -(acac) 2 ] or [V(O)(OiPr) 3 ] is reported. In the former system, the presence of triphenylphosphane oxide allows high conver-

Cited by 44 publications

References 51 publications

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

An Improved and Safer Synthesis of (R)‐ and (S)‐4,4′‐Diaminomethyl‐BINAP

Synthetic Transformations for the Valorization of Fatty Acid Derivatives

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