TY - JOUR
T1 - Oxy-Allyl Cation Catalysis
T2 - An Enantioselective Electrophilic Activation Mode
AU - Liu, Chun
AU - Oblak, E. Zachary
AU - Vander Wal, Mark N.
AU - Dilger, Andrew K.
AU - Almstead, Danielle K.
AU - MacMillan, David W.C.
PY - 2016/3/2
Y1 - 2016/3/2
N2 - A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.
AB - A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event.
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U2 - 10.1021/jacs.5b13041
DO - 10.1021/jacs.5b13041
M3 - Article
C2 - 26797012
AN - SCOPUS:84959378610
VL - 138
SP - 2134
EP - 2137
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 7
ER -