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trans ‐Carbocarbonation of Internal Alkynes through a Formal anti ‐Carbopalladation/C−H Activation Cascade
Author(s) -
Reding Andreas,
Jones Peter G.,
Werz Daniel B.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201805399
Subject(s) - alkyne , chemistry , intramolecular force , silylation , hydride , ring (chemistry) , stereochemistry , catalysis , catalytic cycle , cascade , triple bond , cascade reaction , double bond , reductive elimination , medicinal chemistry , deuterium , hydrogen , organic chemistry , physics , chromatography , quantum mechanics
An intramolecular Pd‐catalyzed cascade reaction is presented that consists of a formal anti ‐carbopalladation of a C−C triple bond followed by C−H activation. As a result, oligocyclic ring systems with an embedded tetrasubstituted double bond are formed. The key to success in affording the trans geometry of the emerging double bond are alkyne units with residues that must not undergo β‐hydride elimination (e.g., t‐butyl or silyl groups). Silyl groups proved to be a perfect handle to further convert the tetrasubstituted alkenes. The evaluation of kinetic data with a deuterium‐labeled compound and X‐ray analyses of trapped intermediates provided additional insight into the catalytic cycle.