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An Efficient Approach to Regio- and Stereodefined Fully-Substituted Alkenylsilanes by Pd-Catalyzed Allenic C(sp(3))-H Oxidation
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0001-8462-4176
Number of Authors: 22019 (English)In: Chemistry: A European Journal, ISSN 0947-6539, Vol. 25, no 49, p. 11566-11573Article in journal (Refereed) Published
Abstract [en]

A highly efficient palladium-catalyzed functionalization of allenylsilanes to give regio- and stereodefined fully-substituted alkenylsilanes has been developed. This oxidative coupling reaction showed good functional group compatibility with exclusive regio- and stereoselectivity. The pending olefin on the silyl group was shown to be an indispensable element for the initial allenic C(sp(3))-H bond cleavage, and performs as the directing group to control the overall selectivity. The addition of substoichiometric amounts of Et3N was found to increase the reaction rate leading to a higher reaction yield. The reaction can be easily scaled up and applied for the late-stage functionalization of natural products and pharmaceutical compounds, including amino acids and steroid derivatives. The newly introduced functional groups include aryl, alkynyl, and boryl groups. The highly strained four-membered ring, silacyclobutene was obtained when B(2)pin(2) was employed as the coupling partner. Mechanistic studies, including kinetic isotope effects, showed that the allenic C(sp(3))-H bond cleavage is the rate-limiting step.

Place, publisher, year, edition, pages
2019. Vol. 25, no 49, p. 11566-11573
Keywords [en]
allenylsilane, oxidation, regioselectivity, stereoselectivity, tetrasubstituted olefins
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-173165DOI: 10.1002/chem.201902962ISI: 000481084400001PubMedID: 31265176OAI: oai:DiVA.org:su-173165DiVA, id: diva2:1353656
Available from: 2019-09-23 Created: 2019-09-23 Last updated: 2019-09-23Bibliographically approved

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