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.
Keywords: carbenes; retro-Buchner reaction; rhodium catalysis; silanes; total synthesis.
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