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Rhodium‐Catalyzed [2+2+2] Cycloadditions of Diynes with Morita–Baylis–Hillman Adducts: A Stereoselective Entry to Densely Functionalized Cyclohexadiene Scaffolds
Author(s) -
Fernández Martí,
Parera Magda,
Parella Teodor,
Lledó Agustí,
Le Bras Jean,
Muzart Jacques,
PlaQuintana Anna,
Roglans Anna
Publication year - 2016
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600039
Subject(s) - chemistry , rhodium , adduct , cycloaddition , stereoselectivity , catalysis , kinetic resolution , medicinal chemistry , stereochemistry , enantioselective synthesis , organic chemistry
A rhodium‐catalyzed asymmetric synthesis of 5,5‐disubstituted cyclohexa‐1,3‐dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita–Baylis–Hillman (M‐B‐H) adducts as unsaturated substrates. Products containing two adjacent chiral centres (quaternary and tertiary, respectively) were obtained with complete diastereoselectivity and high enantioselectivity (84–97%) through a kinetic resolution of the M‐B‐H adduct. Furthermore, these highly substituted cyclohexadienes reacted with dienophiles to afford the corresponding Diels–Alder cycloadducts in good yields.