Premium
Rhodium‐Catalyzed Enantioselective [4+2] Cycloadditions of Vinylcarbenes with Dienes
Author(s) -
Zhang Bowen,
Davies Huw M. L.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914354
Subject(s) - stereocenter , enantioselective synthesis , rhodium , cycloaddition , diastereomer , chemistry , catalysis , diene , kinetic resolution , stereochemistry , medicinal chemistry , organic chemistry , natural rubber
The reaction of 2‐siloxycyclo‐1,3‐dienes with E ‐vinyldiazoacetates in the presence of the bulky chiral dirhodium tetracarboxylate catalyst, Rh 2 ( R ‐ p ‐PhTPCP) 4 results in an enantioselective [4+2] cycloaddition, in which three new stereogenic centers are formed. The [4+2] cycloadducts are generated as single diastereomers with high enantiocontrol (95–98 % ee ). When the diene contains an additional stereogenic center, effective kinetic resolution can be achieved.