Enantiomer-selective activation of racemic catalysts.
Asymmetric catalysts can be evolved into highly activated catalysts by association with chiral activators. This asymmetric activation process is particularly useful in racemic catalysis through selective activation of one enantiomer of the racemic catalysts. Recently, a strategy whereby a racemic catalyst is selectively deactivated by a chiral additive has been reported to yield nonracemic products. However, we have reported a strategy that is an alternative to asymmetric catalysts but is conceptually opposite, in which a chiral activator selectively activates rather than deactivates one enantiomer of a racemic chiral catalyst. The advantage of this activation strategy over the deactivation counterpart is that the activated catalyst can produce a greater enantiomeric excess (x(act)% ee) in the products than the ee attained by the enantiomerically pure catalyst on its own. Therefore, 'asymmetric activation' could provide a general and powerful strategy for the use of not only atropisomeric and, hence, racemic ligands but also chirally flexible and 'pro-atropisomeric' ligands without enantiomeric resolution!
Mikami
K
K
Department of Chemical Technology, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan. kmikami@o.cc.titech.ac.jp
Terada
M
M
Korenaga
T
T
Matsumoto
Y
Y
Matsukawa
S
S
D002384:Catalysis; D007700:Kinetics; D019216:Metals, Heavy / Q000737:chemistry; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
D019216:Metals, Heavy; D009942:Organometallic Compounds; D011083:Polycyclic Compounds