Through‐Bond/Through‐Space Anion Relay Chemistry Exploiting Vinylepoxides as Bifunctional Linchpins1. (16th December 2013)

• Record Type: Journal Article
• Authors: Chen, Ming Z.; Gutierrez, Osvaldo; Smith, Amos B.
• Is Part Of: Angewandte Chemie. Volume 126:Number 5(2014)
• Page Start: 1303
• Page End: 1306
• Publication Date: 2013-12-16
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201309270
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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_N2′ reaction, followed by through‐space ARC exploiting a 1, 4‐Brook rearrangement. The <italic>trans</italic>‐disubstituted vinylepoxide linchpin yields a mixture of <italic>E</italic>/<italic>Z</italic> isomers, whereas the <italic>cis</italic>‐disubstituted and the <italic>trans</italic>‐trisubstituted vinylepoxide linchpins proceed to deliver three‐component adducts with excellent <italic>E</italic> selectivity.</p> </abstract>