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Stereocontrolled Synthesis of Vinyl Boronates and Vinyl Silanes via Atom-Economical Ruthenium-Catalyzed Alkene-Alkyne Coupling.

ABSTRACT: The synthesis of vinyl boronates and vinyl silanes was achieved by employing a Ru-catalyzed alkene-alkyne coupling reaction of allyl boronates or allyl silanes with various alkynes. The double bond geometry in the generated vinyl boronates can be remotely controlled by the juxtaposing boron- and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations, including iterative cross-coupling reactions, and a Chan-Lam-type allyloxylation followed by a Claisen rearrangement. A sequential one-pot alkene-alkyne-coupling/allylation-sequence with an aldehyde to deliver a highly complex ?-silyl-?-hydroxy olefin with a handle for further functionalization was also realized.

SUBMITTER: Trost BM

PROVIDER: S-EPMC4715692 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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Stereocontrolled Synthesis of Vinyl Boronates and Vinyl Silanes via Atom-Economical Ruthenium-Catalyzed Alkene-Alkyne Coupling.

Trost Barry M BM Koester Dennis C DC Herron Alastair N AN

Angewandte Chemie (International ed. in English) 20151117 52

The synthesis of vinyl boronates and vinyl silanes was achieved by employing a Ru-catalyzed alkene-alkyne coupling reaction of allyl boronates or allyl silanes with various alkynes. The double bond geometry in the generated vinyl boronates can be remotely controlled by the juxtaposing boron- and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations, including iterative cross-coupling reactions, and a ...[more]

PMID: 26572804

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