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Synthesis of Linear ( Z )‐α,β‐Unsaturated Esters by Catalytic Cross‐Metathesis. The Influence of Acetonitrile
Author(s) -
Yu Elsie C.,
Johnson Brett M.,
Townsend Erik M.,
Schrock Richard R.,
Hoveyda Amir H.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201608087
Subject(s) - acetonitrile , alkene , metathesis , chemistry , catalysis , natural product , stereoselectivity , combinatorial chemistry , salt metathesis reaction , stereochemistry , organic chemistry , polymerization , polymer
Abstract Kinetically controlled catalytic cross‐metathesis reactions that generate ( Z )‐α,β‐unsaturated esters selectively are disclosed. A key finding is that the presence of acetonitrile obviates the need for using excess amounts of a more valuable terminal alkene substrates. On the basis of X‐ray structure and spectroscopic investigations a rationale for the positive impact of acetonitrile is provided. Transformations leading to various E,Z‐dienoates are highly Z‐selective as well. Utility is highlighted by application to stereoselective synthesis of the C1–C12 fragment of biologically active natural product (−)‐laulimalide.