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Updated: Jan 31, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Donor Rhodium Carbenes by Retro-Buchner Reaction
Mauro Mato1,2, Antonio M Echavarren1,2
1Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Abstract:
Rhodium carbenes are key intermediates in a range of cycloadditions and insertion reactions. Herein, we report the first generation of donor RhII carbenes by decarbenation of 7-substituted 1,3,5-cycloheptatrienes. This discovery unlocks an improved retro-Buchner-cyclopropanation sequence, a Si-H insertion reaction for a broad-scope synthesis of allylsilanes, and a new method for the vinylogation of aldehydes. The last strategy led to the development of an iterative synthesis of E-polyenes, and to the total synthesis of navenones B and C.
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