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"Vokits, Benjamin"
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Decarboxylative alkenylation
by
Knouse, Kyle W.
,
Vokits, Benjamin
,
Qin, Tian
in
639/638/403/933
,
639/638/403/977
,
639/638/77/888
2017
Starting with alkyl carboxylic acids, a simple olefin synthesis using any substitution pattern or geometry, based on amide-bond synthesis with nickel- or iron-based catalysis, is described.
Simplified olefin synthesis
Olefins are ubiquitous functional groups in organic chemistry and are typically installed in small molecules by the formation of a carbon–carbon double bond. Here, Phil Baran and colleagues report a decarboxylative alkyl-vinyl cross-coupling that offers a cheap and simple route to olefins with defined geometry and substitution pattern. The nickel or iron catalysts extract carbon dioxide from the carboxylic acid, which is activated in a similar way to peptide-bond formation. The alkene is then attached with a vinyl zinc reagent. The authors exemplify their method by preparing more than 60 olefins and synthesizing 16 natural products. One such example offers a short route to macrocyclic polyketides from the commodity chemical diethyl tartrate.
Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, has an essential role in the manipulation of organic matter
1
. Despite its importance, olefin synthesis still relies largely on chemistry introduced more than three decades ago, with metathesis
2
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.
Journal Article
Decarboxylative alkenylation
by
Knouse, Kyle W.
,
Vokits, Benjamin
,
Qin, Tian
in
Alkenes
,
Chemical properties
,
Chemical reactions
2017
Journal Article
Decarboxylative alkenylation
by
Knouse, Kyle W.
,
Vokits, Benjamin
,
Qin, Tian
in
Alkenes
,
Chemical properties
,
Chemical reactions
2017
Journal Article
Decarboxylative alkenylation
by
Knouse, Kyle W.
,
Vokits, Benjamin
,
Qin, Tian
in
Alkenes
,
Chemical properties
,
Chemical reactions
2017
Journal Article