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Donor Rhodium Carbenes by Retro‐Buchner Reaction
Author(s) -
Mato Mauro,
Echavarren Antonio M.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813512
Subject(s) - rhodium , cyclopropanation , chemistry , total synthesis , carbene , sequence (biology) , insertion reaction , scope (computer science) , combinatorial chemistry , stereochemistry , catalysis , organic chemistry , computer science , biochemistry , programming language
Rhodium carbenes are key intermediates in a range of cycloadditions and insertion reactions. Herein, we report the first generation of donor Rh II 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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