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 ami...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2007-04, Vol.316 (5824), p.582-585
Main Authors: Beeson, Teresa D, Mastracchio, Anthony, Hong, Jun-Bae, Ashton, Kate, MacMillan, David W.C
Format: Article
Language:English
Subjects:
Activation
Aldehydes
Aldehydes - chemistry
Alkenes
Amines
Amines - chemistry
Asymmetry
Catalysis
Catalysts
Chemical synthesis
Chemistry
Cyclization
Exact sciences and technology
Halogenation
Halogens - chemistry
Hydrocarbons
Ketones
Kinetics and mechanisms
Molecular orbitals
Molecular Structure
Nucleophiles
Organic Chemicals - chemistry
Organic chemistry
Oxidation
Oxidation-Reduction
Radicals
Reactivity and mechanisms
Solvents
Stereoisomerism
Substrates
Synthetic chemistry techniques
Utilities
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Summary: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.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1142696