P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters

Sunewang Rixin Wang; Alexander T. Radosevich

doi:10.1021/acs.orglett.5b01784

P(NMe₂)₃-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters

Sunewang Rixin Wang, Alexander T. Radosevich^*

^*Corresponding author for this work

Pennsylvania State University

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

A commercial phosphorus-based reagent (P(NMe₂)₃) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

Original language	English
Pages (from-to)	3810-3813
Number of pages	4
Journal	Organic Letters
Volume	17
Issue number	15
DOIs	https://doi.org/10.1021/acs.orglett.5b01784
State	Published - 7 Aug 2015
Externally published	Yes

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title = "P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters",

abstract = "A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.",

author = "Wang, \{Sunewang Rixin\} and Radosevich, \{Alexander T.\}",

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year = "2015",

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AU - Wang, Sunewang Rixin

AU - Radosevich, Alexander T.

PY - 2015/8/7

Y1 - 2015/8/7

N2 - A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

AB - A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

UR - https://www.scopus.com/pages/publications/84938824029

U2 - 10.1021/acs.orglett.5b01784

DO - 10.1021/acs.orglett.5b01784

M3 - 文章

C2 - 26176378

AN - SCOPUS:84938824029

SN - 1523-7060

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SP - 3810

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JO - Organic Letters

JF - Organic Letters

IS - 15

ER -

P(NMe₂)₃-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters

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