TY - JOUR
T1 - Direct and enantioselective a-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis
AU - Mastracchio, Anthony
AU - Warkentin, Alexander A.
AU - Walji, Abbas M.
AU - MacMillan, David W.C.
PY - 2010/11/30
Y1 - 2010/11/30
N2 - The first enantioselective organocatalytic a-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective a-enolation and a-carbooxidation of ketones.
AB - The first enantioselective organocatalytic a-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective a-enolation and a-carbooxidation of ketones.
KW - Asymmetric synthesis
KW - Organocatalysis
UR - http://www.scopus.com/inward/record.url?scp=78650543169&partnerID=8YFLogxK
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U2 - 10.1073/pnas.1002845107
DO - 10.1073/pnas.1002845107
M3 - Article
C2 - 20921367
AN - SCOPUS:78650543169
SN - 0027-8424
VL - 107
SP - 20648
EP - 20651
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 48
ER -