Palladium-Catalyzed Synthesis of Dibenzosilepin Derivatives via 1,n-Palladium Migration Coupled with anti-Carbopalladation of Alkyne
- 11 January 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (3), 1641-1650
- https://doi.org/10.1021/jacs.0c12453
Abstract
Catalytic reactions involving 1,n-metal migration represent a powerful method for the synthesis of complex molecules from simple precursors through the activation of C–H bonds. By utilizing this attractive feature, herein we devised a palladium-catalyzed synthesis of new members of 5H-dibenzo[b,f]silepins, a class of underexplored but potentially useful silicon-bridged π-conjugated compounds. The reaction sequence is composed of 1,n-palladium migrations and unusual anti-carbopalladation of alkynes, which was realized by the proper choice of ligand for palladium. A series of deuterium-labeling experiments were conducted toward an understanding of the reaction mechanism to propose plausible catalytic cycles. The newly obtained 5H-dibenzo[b,f]silepins exhibited tunable optical and electronic properties, demonstrating the power and importance of developing a new synthetic method based on 1,n-metal migration processes.Funding Information
- Japan Society for the Promotion of Science (JP20H02741, JP20H04821)
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