A novel B(C6F5)3-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes

Vladimir Gevorgyan, Michael Rubin, Sharonda Benson, Jian Xiu Liu, Yoshinori Yamamoto

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241 Citations (Scopus)

Abstract

The primary alcohols 1a-e and ethers 4a-d were effectively reduced to the corresponding hydrocarbons 2 by HSiEt3 in the presence of catalytic amounts of B(C6F5)3. To the best of our knowledge, this is the first example of catalytic use of Lewis acid in the reduction of alcohols and ethers with hydrosilanes. The secondary alkyl ethers 4j,k enabled cleavage and/or reduction under similar reaction conditions to produce either the silyl ethers 3m-n or the corresponding alcohol 5a upon subsequent deprotection with TBAF. It was found that the secondary alcohols 1g-i and tertiary alcohol 1j, as well as the tertiary alkyl ether 4l, did not react with HSiEt3/(B(C6F5)3 reducing reagent at all. The following relative reactivity order of substrates was found: primary >> secondary > tertiary. A plausible mechanism for this nontraditional Lewis acid catalyzed reaction is proposed.

Original languageEnglish (US)
Pages (from-to)6179-6186
Number of pages8
JournalJournal of Organic Chemistry
Volume65
Issue number19
DOIs
StatePublished - Sep 22 2000
Externally publishedYes

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Ethers
Alcohols
Lewis Acids
Hydrocarbons
Ether
Substrates

ASJC Scopus subject areas

  • Organic Chemistry

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A novel B(C6F5)3-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes. / Gevorgyan, Vladimir; Rubin, Michael; Benson, Sharonda; Liu, Jian Xiu; Yamamoto, Yoshinori.

In: Journal of Organic Chemistry, Vol. 65, No. 19, 22.09.2000, p. 6179-6186.

Research output: Contribution to journalArticle

Gevorgyan, Vladimir ; Rubin, Michael ; Benson, Sharonda ; Liu, Jian Xiu ; Yamamoto, Yoshinori. / A novel B(C6F5)3-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 19. pp. 6179-6186.
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AU - Yamamoto, Yoshinori

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N2 - The primary alcohols 1a-e and ethers 4a-d were effectively reduced to the corresponding hydrocarbons 2 by HSiEt3 in the presence of catalytic amounts of B(C6F5)3. To the best of our knowledge, this is the first example of catalytic use of Lewis acid in the reduction of alcohols and ethers with hydrosilanes. The secondary alkyl ethers 4j,k enabled cleavage and/or reduction under similar reaction conditions to produce either the silyl ethers 3m-n or the corresponding alcohol 5a upon subsequent deprotection with TBAF. It was found that the secondary alcohols 1g-i and tertiary alcohol 1j, as well as the tertiary alkyl ether 4l, did not react with HSiEt3/(B(C6F5)3 reducing reagent at all. The following relative reactivity order of substrates was found: primary >> secondary > tertiary. A plausible mechanism for this nontraditional Lewis acid catalyzed reaction is proposed.

AB - The primary alcohols 1a-e and ethers 4a-d were effectively reduced to the corresponding hydrocarbons 2 by HSiEt3 in the presence of catalytic amounts of B(C6F5)3. To the best of our knowledge, this is the first example of catalytic use of Lewis acid in the reduction of alcohols and ethers with hydrosilanes. The secondary alkyl ethers 4j,k enabled cleavage and/or reduction under similar reaction conditions to produce either the silyl ethers 3m-n or the corresponding alcohol 5a upon subsequent deprotection with TBAF. It was found that the secondary alcohols 1g-i and tertiary alcohol 1j, as well as the tertiary alkyl ether 4l, did not react with HSiEt3/(B(C6F5)3 reducing reagent at all. The following relative reactivity order of substrates was found: primary >> secondary > tertiary. A plausible mechanism for this nontraditional Lewis acid catalyzed reaction is proposed.

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