Prev. Article Next Article Table of Contents

Article

Direct Reduction of Alcohols: Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride

Supporting Info

Makoto Yasuda, Yoshiyuki Onishi, Masako Ueba, Takashi Miyai, and Akio Baba*

Department of Molecular Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

J. Org. Chem., 2001, 66 (23), pp 7741–7744

DOI: 10.1021/jo0158534

Publication Date (Web): September 29, 2001

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, baba@ap.chem.eng.osaka-u.ac.jp

Abstract

The direct reduction of alcohols using chlorodiphenylsilane as a hydride source in the presence of a catalytic amount of indium trichloride is described. Benzylic alcohols, secondary alcohols, and tertiary alcohols were effectively reduced to give the corresponding alkanes in high yields. A compound bearing both primary and secondary hydroxyl groups was reduced only at the secondary site to afford the primary alcohol after workup with Bu₄NF. This system showed high chemoselectivity only for the hydroxyl group while not reducing other functional groups that are readily reduced by standard reducing systems. Thus alcohols bearing ester, chloro, bromo, or nitro groups, which are sensitive to LiAlH₄ or Zn/H⁺, were selectively reduced only at the hydroxyl sites by the chlorodiphenylsilane/InCl₃ system. NMR studies revealed the reaction course. The hydrodiphenylsilyl ether is initially formed and then, with InCl₃ acting as a Lewis acid, forms an oxonium complex, which accelerates the desiloxylation with donation of the hydrogen to the carbon.

View: Full Text HTML | Hi-Res PDF

Tools

SciFinder Links

History

Published In Issue November 16, 2001
Received June 21, 2001

Recommend & Share

Related Content

Iridium-Catalyzed Addition of Acid Chlorides to Terminal AlkynesJournal of the American Chemical Society
- Iridium-Catalyzed Addition of Acid Chlorides to Terminal Alkynes
  Tomohiro Iwai, Tetsuaki Fujihara, Jun Terao and Yasushi Tsuji
  Journal of the American Chemical Society 2009 131 (19), pp 6668–6669
  Abstract: An iridium N-heterocyclic carbene (NHC) complex, IrCl(cod)(IPr), successfully catalyzed an addition of common aromatic acid chlorides to terminal alkynes to afford (Z)-β-chloro-α,β-unsaturated ketones regio- and stereoselectively. When the NHC ligand (IPr)...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF
Multicatalytic Synthesis of α-Pyrrolidinyl Ketones via a Tandem Palladium(II)/Indium(III)-Catalyzed Aminochlorocarbonylation/Friedel−Crafts Acylation ReactionJournal of the American Chemical Society
- Multicatalytic Synthesis of α-Pyrrolidinyl Ketones via a Tandem Palladium(II)/Indium(III)-Catalyzed Aminochlorocarbonylation/Friedel−Crafts Acylation Reaction
  Tim A. Cernak and Tristan H. Lambert
  Journal of the American Chemical Society 2009 131 (9), pp 3124–3125
  Abstract: An oxidative carbonylation reaction that generates acid chloride functionality has been developed. Furthermore, this aminochlorocarbonylation reaction has been merged with a catalytic Friedel−Crafts acylation to produce a highly efficient tandem ...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF
In(III)-Mediated Chemoselective Dehydrogenative Interaction of ClMe₂SiH with Carboxylic Acids: Direct Chemo- and Regioselective Friedel−Crafts Acylation of Aromatic EthersOrganic Letters
- In(III)-Mediated Chemoselective Dehydrogenative Interaction of ClMe₂SiH with Carboxylic Acids: Direct Chemo- and Regioselective Friedel−Crafts Acylation of Aromatic Ethers
  Srinivasarao Arulananda Babu, Makoto Yasuda, and Akio Baba
  Organic Letters 2007 9 (3), pp 405–408
  Abstract: Chemoselective dehydrogenative interaction of ClMe₂SiH with a carboxylic acid group in the presence of InX₃ is reported. ¹³C NMR investigation revealed the formation of PhCOOSi(Cl)Me₂ as the major transient intermediate. Chemo- and regioselective Friedel−...
  Abstract | Full Text HTML | Hi-Res PDF

Article

Direct Reduction of Alcohols: Highly Chemoselective Reducing System for Secondary or Tertiary Alcohols Using Chlorodiphenylsilane with a Catalytic Amount of Indium Trichloride