Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones

Jun Wu; Yuhai Tang; Wen Wei; Yong Wu; Yang Li; Junjie Zhang; Yuansuo Zheng; Silong Xu

doi:10.1002/anie.201800555

Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones

Jun Wu
, Yuhai Tang
, Wen Wei
, Yong Wu
, Yang Li
, Junjie Zhang
, Yuansuo Zheng
, Silong Xu

School of Chemistry

Xi'an Jiaotong University

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

68 Scopus citations

Abstract

We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C₅ synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig S_N2′ ring closure.

Original language	English
Pages (from-to)	6284-6288
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	21
DOIs	https://doi.org/10.1002/anie.201800555
State	Published - 22 May 2018

Keywords

cycloheptenones
organocatalysis
phosphine catalysis
rearrangement
vinylcyclopropanes

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10.1002/anie.201800555

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title = "Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones",

abstract = "We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C5 synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig SN2′ ring closure.",

keywords = "cycloheptenones, organocatalysis, phosphine catalysis, rearrangement, vinylcyclopropanes",

author = "Jun Wu and Yuhai Tang and Wen Wei and Yong Wu and Yang Li and Junjie Zhang and Yuansuo Zheng and Silong Xu",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

month = may,

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doi = "10.1002/anie.201800555",

language = "英语",

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T1 - Phosphine-Catalyzed Activation of Vinylcyclopropanes

T2 - Rearrangement of Vinylcyclopropylketones to Cycloheptenones

AU - Wu, Jun

AU - Tang, Yuhai

AU - Wei, Wen

AU - Wu, Yong

AU - Li, Yang

AU - Zhang, Junjie

AU - Zheng, Yuansuo

AU - Xu, Silong

PY - 2018/5/22

Y1 - 2018/5/22

N2 - We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C5 synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig SN2′ ring closure.

AB - We report a phosphine-catalyzed activation of electron-deficient vinylcyclopropanes (VCPs) to generate an ambident C5 synthon that is poised to undergo consecutive reactions. The utility of the activation is demonstrated in a phosphine-catalyzed rearrangement of vinylcyclopropylketones to cycloheptenones in good yields with a broad substrate scope. Mechanistic investigations support a stepwise process comprising homoconjugate addition, water-assisted proton transfer, and 7-endo-trig SN2′ ring closure.

KW - cycloheptenones

KW - organocatalysis

KW - phosphine catalysis

KW - rearrangement

KW - vinylcyclopropanes

UR - https://www.scopus.com/pages/publications/85046126430

U2 - 10.1002/anie.201800555

DO - 10.1002/anie.201800555

M3 - 文章

C2 - 29645401

AN - SCOPUS:85046126430

SN - 1433-7851

VL - 57

SP - 6284

EP - 6288

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 21

ER -

Phosphine-Catalyzed Activation of Vinylcyclopropanes: Rearrangement of Vinylcyclopropylketones to Cycloheptenones

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Keywords

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