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Through-bond/through-space anion relay chemistry exploiting vinylepoxides as bifunctional linchpins.

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 SN 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.

SUBMITTER: Chen MZ

PROVIDER: S-EPMC3969824 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Through-bond/through-space anion relay chemistry exploiting vinylepoxides as bifunctional linchpins.

Chen Ming Z MZ Gutierrez Osvaldo O Smith Amos B AB

Angewandte Chemie (International ed. in English) 20131216 5

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 SN 2' reaction, followed by through-space ARC exploiting a 1,4-Brook rearrangement. The trans-disubstitu ...[more]

PMID: 24375870

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