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Highly Stereospecific Cyclizations of Homoallylic Silanols
Shinde, Anand H. Dhokale, Ranjeet A. Mague, Joel T. Sathyamoorthi, Shyam
Shinde, Anand H.
Dhokale, Ranjeet A.
Mague, Joel T.
Sathyamoorthi, Shyam
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Abstract
We demonstrate that di-tert-butylsilanols are competent nucleophiles for the intramolecular interception of palladium π-allyl species. In these reactions, allyl ethyl carbonates are the best precursors for the formation of palladium π-allyl intermediates, and [(Cinnamyl)PdCl]2/BINAP is superior to other Pd salt/ligand framework combinations. Our optimized protocol is compatible with a variety of silanol substrates. Importantly, the cyclization is perfectly stereospecific, proceeding via an anti-syn mechanism, which stands in contrast to reported analogous reactions of alcohols and phenols, known to proceed via an anti-anti mechanism. The alkenes in the product dioxasilinanes serve as blank slates for further functionalization.
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, Copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.2c01170.
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2022-07-28
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American Chemical Society
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Shinde, A. H., Dhokale, R. A., Mague, J. T., & Sathyamoorthi, S. (2022). Highly Stereospecific Cyclizations of Homoallylic Silanols. The Journal of organic chemistry, 87(16), 11237–11252. https://doi.org/10.1021/acs.joc.2c01170