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Assembly of Complex 1,4‐Cycloheptadienes by (4+3) Cycloaddition of Rhodium(II) and Gold(I) Non‐Acceptor Carbenes
Author(s) -
ArmengolRelats Helena,
Mato Mauro,
Echavarren Antonio M.
Publication year - 2021
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.202012092
Subject(s) - cycloaddition , rhodium , acceptor , chemistry , diene , derivative (finance) , stereochemistry , catalysis , medicinal chemistry , organic chemistry , physics , natural rubber , financial economics , economics , condensed matter physics
The formal (4+3) cycloaddition of 1,3‐dienes with Rh(II) and Au(I) non‐acceptor vinyl carbenes, generated from vinylcycloheptatrienes or alkoxyenynes, respectively, leads to 1,4‐cycloheptadienes featuring complex and diverse substitution patterns, including natural dyctiopterene C′ and a hydroxylated derivative of carota‐1,4‐diene. A complete mechanistic picture is presented, in which Au(I) and Rh(II) non‐acceptor vinyl carbenes were shown to undergo a vinylcyclopropanation/Cope rearrangement or a direct (4+3) cycloaddition that takes place in a non‐concerted manner.