Decarboxylative alkenylation

Jacob T. Edwards, Rohan R. Merchant, Kyle S. McClymont, Kyle W. Knouse, Tian Qin, Lara R. Malins, Benjamin Vokits, Scott A. Shaw, Deng Hui Bao, Fu Liang Wei, Ting Zhou, Martin D. Eastgate, Phil S. Baran

Research output: Contribution to journalArticle

116 Citations (Scopus)

Abstract

Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.

Original languageEnglish (US)
Pages (from-to)213-218
Number of pages6
JournalNature
Volume545
Issue number7653
DOIs
StatePublished - May 11 2017
Externally publishedYes

Fingerprint

Alkenes
Carboxylic Acids
Nickel
Biological Products
Catalysis
Carbon Dioxide
Amides
Polymerization
Iron

ASJC Scopus subject areas

  • General

Cite this

Edwards, J. T., Merchant, R. R., McClymont, K. S., Knouse, K. W., Qin, T., Malins, L. R., ... Baran, P. S. (2017). Decarboxylative alkenylation. Nature, 545(7653), 213-218. https://doi.org/10.1038/nature22307

Decarboxylative alkenylation. / Edwards, Jacob T.; Merchant, Rohan R.; McClymont, Kyle S.; Knouse, Kyle W.; Qin, Tian; Malins, Lara R.; Vokits, Benjamin; Shaw, Scott A.; Bao, Deng Hui; Wei, Fu Liang; Zhou, Ting; Eastgate, Martin D.; Baran, Phil S.

In: Nature, Vol. 545, No. 7653, 11.05.2017, p. 213-218.

Research output: Contribution to journalArticle

Edwards, JT, Merchant, RR, McClymont, KS, Knouse, KW, Qin, T, Malins, LR, Vokits, B, Shaw, SA, Bao, DH, Wei, FL, Zhou, T, Eastgate, MD & Baran, PS 2017, 'Decarboxylative alkenylation', Nature, vol. 545, no. 7653, pp. 213-218. https://doi.org/10.1038/nature22307
Edwards JT, Merchant RR, McClymont KS, Knouse KW, Qin T, Malins LR et al. Decarboxylative alkenylation. Nature. 2017 May 11;545(7653):213-218. https://doi.org/10.1038/nature22307
Edwards, Jacob T. ; Merchant, Rohan R. ; McClymont, Kyle S. ; Knouse, Kyle W. ; Qin, Tian ; Malins, Lara R. ; Vokits, Benjamin ; Shaw, Scott A. ; Bao, Deng Hui ; Wei, Fu Liang ; Zhou, Ting ; Eastgate, Martin D. ; Baran, Phil S. / Decarboxylative alkenylation. In: Nature. 2017 ; Vol. 545, No. 7653. pp. 213-218.
@article{9e6c24e3c7d7473f95b1c6329fc49fb5,
title = "Decarboxylative alkenylation",
abstract = "Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.",
author = "Edwards, {Jacob T.} and Merchant, {Rohan R.} and McClymont, {Kyle S.} and Knouse, {Kyle W.} and Tian Qin and Malins, {Lara R.} and Benjamin Vokits and Shaw, {Scott A.} and Bao, {Deng Hui} and Wei, {Fu Liang} and Ting Zhou and Eastgate, {Martin D.} and Baran, {Phil S.}",
year = "2017",
month = "5",
day = "11",
doi = "10.1038/nature22307",
language = "English (US)",
volume = "545",
pages = "213--218",
journal = "Nature",
issn = "0028-0836",
publisher = "Nature Publishing Group",
number = "7653",

}

TY - JOUR

T1 - Decarboxylative alkenylation

AU - Edwards, Jacob T.

AU - Merchant, Rohan R.

AU - McClymont, Kyle S.

AU - Knouse, Kyle W.

AU - Qin, Tian

AU - Malins, Lara R.

AU - Vokits, Benjamin

AU - Shaw, Scott A.

AU - Bao, Deng Hui

AU - Wei, Fu Liang

AU - Zhou, Ting

AU - Eastgate, Martin D.

AU - Baran, Phil S.

PY - 2017/5/11

Y1 - 2017/5/11

N2 - Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.

AB - Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis being the most recent addition. Here we describe a simple method of accessing olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The activating principles used in amide-bond synthesis can therefore be used, with nickel- or iron-based catalysis, to extract carbon dioxide from a carboxylic acid and economically replace it with an organozinc-derived olefin on a molar scale. We prepare more than 60 olefins across a range of substrate classes, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of 16 different natural products across 10 different families.

UR - http://www.scopus.com/inward/record.url?scp=85019263794&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85019263794&partnerID=8YFLogxK

U2 - 10.1038/nature22307

DO - 10.1038/nature22307

M3 - Article

C2 - 28424520

AN - SCOPUS:85019263794

VL - 545

SP - 213

EP - 218

JO - Nature

JF - Nature

SN - 0028-0836

IS - 7653

ER -