Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes

Valerio Fasano; Liam D. Curless; James E. Radcliffe; Michael J. Ingleson

doi:10.1002/anie.201705100

Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes

Valerio Fasano, Liam D. Curless, James E. Radcliffe, Michael J. Ingleson^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in this study, alkyne 1,2-hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2-hydrocarbation.

Original language	English
Pages (from-to)	9202-9206
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	31
Early online date	4 Jul 2017
DOIs	https://doi.org/10.1002/anie.201705100
Publication status	Published - 24 Jul 2017

Keywords

1,2-hydrocarbation
alkynes
carbocations
frustrated Lewis pairs
hydride transfer

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title = "Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes",

abstract = "Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in this study, alkyne 1,2-hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2-hydrocarbation.",

keywords = "1,2-hydrocarbation, alkynes, carbocations, frustrated Lewis pairs, hydride transfer",

author = "Valerio Fasano and Curless, {Liam D.} and Radcliffe, {James E.} and Ingleson, {Michael J.}",

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AU - Fasano, Valerio

AU - Curless, Liam D.

AU - Radcliffe, James E.

AU - Ingleson, Michael J.

PY - 2017/7/24

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N2 - Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in this study, alkyne 1,2-hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2-hydrocarbation.

AB - Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in this study, alkyne 1,2-hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2-hydrocarbation.

KW - 1,2-hydrocarbation

KW - alkynes

KW - carbocations

KW - frustrated Lewis pairs

KW - hydride transfer

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Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes

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