Oxidative Umpolung α‐Alkylation of Ketones

O. Svetlana  Shneider; Evgeni Pisarevsky; Peter Fristrup; Alex M.  Szpilman

doi:10.1021/ol503384c

Oxidative Umpolung α‐Alkylation of Ketones

O. Svetlana Shneider, Evgeni Pisarevsky, Peter Fristrup, Alex M. Szpilman

Department of Chemistry

Technion-Israel Institute of Technology

Research output: Contribution to journal › Journal article › Research › peer-review

Abstract

We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMR
studies, trapping and crossover experiments, and computational studies.

Original language	English
Journal	Organic Letters
Volume	17
Issue number	2
Pages (from-to)	282-285
Number of pages	4
ISSN	1523-7060
DOIs	https://doi.org/10.1021/ol503384c
Publication status	Published - 2015

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abstract = "We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMRstudies, trapping and crossover experiments, and computational studies.",

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PY - 2015

Y1 - 2015

N2 - We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMRstudies, trapping and crossover experiments, and computational studies.

AB - We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMRstudies, trapping and crossover experiments, and computational studies.

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DO - 10.1021/ol503384c

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JO - Organic Letters

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Oxidative Umpolung α‐Alkylation of Ketones

Abstract

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