Enantioselective organocatalysis using SOMO activation.
The asymmetric α-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective α-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.
Beeson
Teresa D
TD
Merck Center for Catalysis, Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.
Mastracchio
Anthony
A
Hong
Jun-Bae
JB
Ashton
Kate
K
Macmillan
David W C
DW
D000447:Aldehydes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D006219:Halogens / Q000737:chemistry; D015394:Molecular Structure; D009930:Organic Chemicals / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D000447:Aldehydes; D000588:Amines; D006219:Halogens; D009930:Organic Chemicals