Acrylate Metathesis via the Second-Generation Grubbs Catalyst: Unexpected Pathways Enabled by a PCy3-Generated Enolate

Gwendolyn A. Bailey; Deryn E. Fogg

doi:10.1021/jacs.5b04524

Acrylate Metathesis via the Second-Generation Grubbs Catalyst: Unexpected Pathways Enabled by a PCy₃-Generated Enolate

Gwendolyn A. Bailey
, Deryn E. Fogg

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

41 Scopus citations

Abstract

The diverse applications of acrylate metathesis range from synthesis of high-value α,β-unsaturated esters to depolymerization of unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack of PCy₃ on the acrylate olefin to generate a reactive carbanion, which participates in multiple pathways, including further Michael addition, proton abstraction, and catalyst deactivation. Related chemistry may be anticipated whenever labile metal-phosphine complexes are used to catalyze reactions of substrates bearing an electron-deficient olefin.

Original language	English (US)
Pages (from-to)	7318-7321
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	23
DOIs	https://doi.org/10.1021/jacs.5b04524
State	Published - Jun 17 2015
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

Publisher link

10.1021/jacs.5b04524

Find It

Find It at U of M Libraries

Cite this

@article{6aab989ff77f4cfe86727f90c3f0867a,

title = "Acrylate Metathesis via the Second-Generation Grubbs Catalyst: Unexpected Pathways Enabled by a PCy3-Generated Enolate",

abstract = "The diverse applications of acrylate metathesis range from synthesis of high-value α,β-unsaturated esters to depolymerization of unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack of PCy3 on the acrylate olefin to generate a reactive carbanion, which participates in multiple pathways, including further Michael addition, proton abstraction, and catalyst deactivation. Related chemistry may be anticipated whenever labile metal-phosphine complexes are used to catalyze reactions of substrates bearing an electron-deficient olefin.",

author = "Bailey, \{Gwendolyn A.\} and Fogg, \{Deryn E.\}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = jun,

day = "17",

doi = "10.1021/jacs.5b04524",

language = "English (US)",

volume = "137",

pages = "7318--7321",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Acrylate Metathesis via the Second-Generation Grubbs Catalyst

T2 - Unexpected Pathways Enabled by a PCy3-Generated Enolate

AU - Bailey, Gwendolyn A.

AU - Fogg, Deryn E.

PY - 2015/6/17

Y1 - 2015/6/17

N2 - The diverse applications of acrylate metathesis range from synthesis of high-value α,β-unsaturated esters to depolymerization of unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack of PCy3 on the acrylate olefin to generate a reactive carbanion, which participates in multiple pathways, including further Michael addition, proton abstraction, and catalyst deactivation. Related chemistry may be anticipated whenever labile metal-phosphine complexes are used to catalyze reactions of substrates bearing an electron-deficient olefin.

AB - The diverse applications of acrylate metathesis range from synthesis of high-value α,β-unsaturated esters to depolymerization of unsaturated polymers. Examined here are unexpected side reactions promoted by the important Grubbs catalyst GII. Evidence is presented for attack of PCy3 on the acrylate olefin to generate a reactive carbanion, which participates in multiple pathways, including further Michael addition, proton abstraction, and catalyst deactivation. Related chemistry may be anticipated whenever labile metal-phosphine complexes are used to catalyze reactions of substrates bearing an electron-deficient olefin.

UR - https://www.scopus.com/pages/publications/84934991967

UR - https://www.scopus.com/pages/publications/84934991967#tab=citedBy

U2 - 10.1021/jacs.5b04524

DO - 10.1021/jacs.5b04524

M3 - Article

AN - SCOPUS:84934991967

SN - 0002-7863

VL - 137

SP - 7318

EP - 7321

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -