A New Solvent‐Free Reaction for the Preparation of Alkoxysilane from Cyclic Ethers, Alcohols, or Carbonyl Compounds

Pehlivan, Leyla; Métay, Estelle; Boyron, Olivier; Demonchaux, Patrice; Mignani, Gérard; Lemaire, Marc

doi:10.1002/ejoc.201100489

Cited by 24 publications

(10 citation statements)

References 43 publications

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“…131), hexane oxide gave a mixture of isomeric silylated alcohols. 114 Tetrahydrofurans also gave alkoxysilanes via a reductive ring opening (Eq. 132).…”

Section: Miscellaneous Tmds Reductionsmentioning

confidence: 99%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

103

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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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“…131), hexane oxide gave a mixture of isomeric silylated alcohols. 114 Tetrahydrofurans also gave alkoxysilanes via a reductive ring opening (Eq. 132).…”

Section: Miscellaneous Tmds Reductionsmentioning

confidence: 99%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

103

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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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“…Lemaire and co‐workers applied a catalytic system of Pd/C ( 11 )/TMDS for the high‐yielding hydrosilylation of epoxides (Scheme ) . The hydrosilylation of epoxides with TMDS (0.5 equiv) in the presence of 11 (1.2 mol %) proceeded under neat conditions to give the corresponding silyl‐protected alcohols.…”

Section: Hydrosilylative Reduction Of Epoxidesmentioning

confidence: 99%

“…[35] Lemaire and co-workers applied ac atalytic system of Pd/C (11)/TMDS for the high-yielding hydrosilylation of epoxides (Scheme 21). [36] The hydrosilylationo fe poxides with TMDS (0.5 equiv) in the presence of 11 (1.2mol %) proceeded under neat conditions to give the corresponding silyl-protected alcohols. Although the reaction of styrene oxide wasq uantitative and selective, to give the alkoxydisiloxane in excellent yield, 1,2-epoxyhexane was converted into as tatistical mixture of three hydrosilylative products in ac ombined yield of 99 %.…”

Section: Hydrosilylative Reduction Of Epoxidesmentioning

confidence: 99%

Catalytic Reduction of Cyclic Ethers with Hydrosilanes

Park

2019

Chemistry An Asian Journal

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Catalytic reductive transformations of ethers as a synthetic building block are an important class of chemical reactions because a range of essential chemical feedstocks and fuels in contemporary life can be prepared through the key step of ethereal C−O bond cleavage of cellulosic biomass. Although conventional stoichiometric and catalytic methods for sp2‐ and sp3‐C−O bond cleavage of linear ethers and alcohols with hydrosilanes are well established, silylative ring opening of cyclic ethers has been less highlighted in this context. This review outlines catalytic systems for the silylative reduction of a range of cyclic ethers, including epoxides and sugars, leading to the corresponding alcohols and/or hydrocarbons. The chemical reactivity and selectivity of these ring‐opening catalytic processes are discussed with respect to the type of substrates; the representative catalytic working modes are also described.

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A New Solvent‐Free Reaction for the Preparation of Alkoxysilane from Cyclic Ethers, Alcohols, or Carbonyl Compounds

Cited by 24 publications

References 43 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

Catalytic Reduction of Cyclic Ethers with Hydrosilanes

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