Prev. Article Next Article Table of Contents

Article

Nonionic Superbase-Catalyzed Silylation of Alcohols

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

PDF/HTML,
figures/images,
references and tables,
(where available)

Bosco A. D'Sa, Dale McLeod, and John G. Verkade*

Department of Chemistry, Iowa State University, Ames, Iowa 50011

J. Org. Chem., 1997, 62 (15), pp 5057–5061

DOI: 10.1021/jo9701492

Publication Date (Web): July 25, 1997

Section:

Organometallic and Organometalloidal Compounds

Abstract

Herein we report a very effective and mild procedure for the silyl protection of a wide variety of substrate alcohols, including primary, secondary, allylic, propargylic, benzylic, hindered secondary, tertiary, acid-sensitive, and base-sensitive alcohols and also hindered phenols. The silylation reagent used is tert-butyldimethylsilyl chloride (TBDMSCl) and the catalyst is P(MeNCH₂CH₂)₃N, 1b, both of which are commercially available. The reactions are carried out in acetonitrile from 24 to 40 °C and on rare occasions in DMF from 24 to 80 °C. The effect of solvent, catalyst concentration, and temperature and reaction time on the silylation of alcohols and the excellent compatibility of our method with a variety of functional groups is discussed. An efficient method for recycling the catalyst is also presented. Although representative primary alcohols, secondary alcohols, and phenols were silylated using the more sterically hindered reagent tert-butyldiphenylsilyl chloride (TBDPSCl) in the presence of 1b as a catalyst, tertiary alcohols were recovered unchanged.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Citing Articles

View all 26 citing articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 13 ACS Journal articles (5 most recent appear below).

P(PhCH₂NCH₂CH₂)₃N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone
Venkat Reddy Chintareddy, Kuldeep Wadhwa and John G. Verkade
The Journal of Organic Chemistry2009 74 (21), 8118-8132
- P(PhCH₂NCH₂CH₂)₃N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone
  Venkat Reddy Chintareddy, Kuldeep Wadhwa and John G. Verkade
  The Journal of Organic Chemistry2009 74 (21), 8118-8132
  Herein we find that proazaphosphatrane 1c is a very efficient catalyst for Mukaiyama aldol reactions of aldehydes with trimethylsilyl enolates in THF solvent. Only the activated ketone 2,2,2-trifluoroacetophenone underwent clean aldol product formation ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
P(PhCH₂NCH₂CH₂)₃N: An Efficient Lewis Base Catalyst for the Synthesis of Propargylic Alcohols and Morita−Baylis−Hillman Adducts via Aldehyde Alkynylation
Kuldeep Wadhwa, Venkat Reddy Chintareddy and John G. Verkade
The Journal of Organic Chemistry2009 74 (17), 6681-6690
- P(PhCH₂NCH₂CH₂)₃N: An Efficient Lewis Base Catalyst for the Synthesis of Propargylic Alcohols and Morita−Baylis−Hillman Adducts via Aldehyde Alkynylation
  Kuldeep Wadhwa, Venkat Reddy Chintareddy and John G. Verkade
  The Journal of Organic Chemistry2009 74 (17), 6681-6690
  Proazaphosphatrane P(PhCH2NCH2CH2)3N (1a) is an efficient catalyst for the addition of aryl trimethylsilyl alkynes to a variety of aromatic, aliphatic, and heterocyclic aldehydes in THF at room temperature. The reaction conditions are mild and employ a ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
P(i-PrNCH₂CH₂)₃N as a Lewis Base Catalyst for the Synthesis of β-Hydroxynitriles Using TMSAN
Kuldeep Wadhwa and John G. Verkade
The Journal of Organic Chemistry2009 74 (15), 5683-5686
- P(i-PrNCH₂CH₂)₃N as a Lewis Base Catalyst for the Synthesis of β-Hydroxynitriles Using TMSAN
  Kuldeep Wadhwa and John G. Verkade
  The Journal of Organic Chemistry2009 74 (15), 5683-5686
  Proazaphosphatrane 1a was found to be an efficient catalyst for synthesis of β-hydroxynitriles via the reaction of trimethylsilylacetonitrile (TMSAN) with aldehydes under mild reaction conditions and typically low catalyst loading (ca. 2 mol %). A variety ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
P(i-PrNCH₂CH₂)₃N: Efficient Catalyst for Synthesizing β-Hydroxyesters and α,β-Unsaturated Esters using α-Trimethylsilylethylacetate (TMSEA)
Kuldeep Wadhwa and John G. Verkade
The Journal of Organic Chemistry2009 74 (11), 4368-4371
- P(i-PrNCH₂CH₂)₃N: Efficient Catalyst for Synthesizing β-Hydroxyesters and α,β-Unsaturated Esters using α-Trimethylsilylethylacetate (TMSEA)
  Kuldeep Wadhwa and John G. Verkade
  The Journal of Organic Chemistry2009 74 (11), 4368-4371
  We present an efficient synthesis of β-hydroxyesters and α,β-unsaturated esters via activation of the silicon−carbon bond of α-trimethylsilylethylacetate using catalytic amounts of the commercially available P(i-PrNCH2CH2)3N 1a. Selectivity for either ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Metal-Dependent Reactions of Bulky Metal(II) Amides M[N(SiMe₃)₂]₂ with 3,3′-Disubstituted Binaphthols (HO)₂C₂₀H₁₀(SiR₃)₂-3,3′: Selective Conversion of One Equivalent −OH Group to a Silyl Ether −OSiMe₃
Anthony E. Wetherby, Jr., Lindy R. Goeller, Antonio G. DiPasquale, Arnold L. Rheingold and Charles S. Weinert
Inorganic Chemistry2008 47 (6), 2162-2170
- Metal-Dependent Reactions of Bulky Metal(II) Amides M[N(SiMe₃)₂]₂ with 3,3′-Disubstituted Binaphthols (HO)₂C₂₀H₁₀(SiR₃)₂-3,3′: Selective Conversion of One Equivalent −OH Group to a Silyl Ether −OSiMe₃
  Anthony E. Wetherby, Jr., Lindy R. Goeller, Antonio G. DiPasquale, Arnold L. Rheingold and Charles S. Weinert
  Inorganic Chemistry2008 47 (6), 2162-2170
  The outcome of the reaction of M[N(SiMe3)2]2·nTHF (M = Be, Zn, Ge, Sn, n = 0; M = Mg, Ca, n = 2) with 3,3′-disubstituted binaphthols (HO)2C20H20(SiR3)2-3,3′ (SiR3 = SiMe3 or SiMe2Ph) depends on the identity of the metal, resulting in selective silylation ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

Tools

SciFinder Links

Explore by:

Author of this Article Any Author Research Topic

History

Published In Issue July 25, 1997
Received January 27, 1997

Select a CAS section from the 5 main topical divisions below:

Article

Nonionic Superbase-Catalyzed Silylation of Alcohols

Abstract

Citing Articles

P(PhCH₂NCH₂CH₂)₃N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone

P(PhCH₂NCH₂CH₂)₃N Catalysis of Mukaiyama Aldol Reactions of Aliphatic, Aromatic, and Heterocyclic Aldehydes and Trifluoromethyl Phenyl Ketone

P(PhCH₂NCH₂CH₂)₃N: An Efficient Lewis Base Catalyst for the Synthesis of Propargylic Alcohols and Morita−Baylis−Hillman Adducts via Aldehyde Alkynylation

P(PhCH₂NCH₂CH₂)₃N: An Efficient Lewis Base Catalyst for the Synthesis of Propargylic Alcohols and Morita−Baylis−Hillman Adducts via Aldehyde Alkynylation

P(i-PrNCH₂CH₂)₃N as a Lewis Base Catalyst for the Synthesis of β-Hydroxynitriles Using TMSAN

P(i-PrNCH₂CH₂)₃N as a Lewis Base Catalyst for the Synthesis of β-Hydroxynitriles Using TMSAN

P(i-PrNCH₂CH₂)₃N: Efficient Catalyst for Synthesizing β-Hydroxyesters and α,β-Unsaturated Esters using α-Trimethylsilylethylacetate (TMSEA)

P(i-PrNCH₂CH₂)₃N: Efficient Catalyst for Synthesizing β-Hydroxyesters and α,β-Unsaturated Esters using α-Trimethylsilylethylacetate (TMSEA)

Metal-Dependent Reactions of Bulky Metal(II) Amides M[N(SiMe₃)₂]₂ with 3,3′-Disubstituted Binaphthols (HO)₂C₂₀H₁₀(SiR₃)₂-3,3′: Selective Conversion of One Equivalent −OH Group to a Silyl Ether −OSiMe₃