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Through‐Bond/Through‐Space Anion Relay Chemistry Exploiting Vinylepoxides as Bifunctional Linchpins
Author(s) -
Chen Ming Z.,
Gutierrez Osvaldo,
Smith Amos B.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201309270
Subject(s) - bifunctional , chemistry , arc (geometry) , adduct , ion , relay , combinatorial chemistry , space (punctuation) , selectivity , organic chemistry , computer science , catalysis , physics , mathematics , power (physics) , geometry , quantum mechanics , operating system
Abstract The development of new bifunctional linchpins that permit the union of diverse building blocks is essential for the synthetic utility of anion relay chemistry (ARC). The design, synthesis, and validation of three vinylepoxide linchpins for through‐bond/through‐space ARC are now reported. For negative charge migration, this class of bifunctional linchpins employs initial through‐bond ARC by an S N 2′ reaction, followed by through‐space ARC exploiting a 1,4‐Brook rearrangement. The trans ‐disubstituted vinylepoxide linchpin yields a mixture of E / Z isomers, whereas the cis ‐disubstituted and the trans ‐trisubstituted vinylepoxide linchpins proceed to deliver three‐component adducts with excellent E selectivity.