Mechanistic Complexity in Organo-SOMO Activation
نویسندگان
چکیده
منابع مشابه
Mechanistic complexity in organo-SOMO activation.
Singly occupied molecular orbital (SOMO) activation provides a pathway for asymmetric a-addition to aldehydes. The scope of SOMO activation includes the allylation, enolation, vinylation, styrenation, chlorination, polyene cyclization, and arylation of a range of aldehydes. This union of organocatalysis with single-electron oxidative coupling is an intricate process involving the complex balanc...
متن کاملEnantioselective polyene cyclization via organo-SOMO catalysis.
The first organocatalytic enantioselective radical polycyclization has been accomplished using singly occupied molecular orbital (SOMO) catalysis. The presented strategy relies on a selective single-electron oxidation of chiral enamines formed by condensation of polyenals with an imidazolidinone catalyst employing a suitable copper(II) oxidant. The reaction proceeds under mildly acidic conditio...
متن کاملEnantioselective organo-SOMO cascade cycloadditions: a rapid approach to molecular complexity from simple aldehydes and olefins.
A highly selective, radical-mediated (4 + 2) coupling reaction of aldehydes and conjugated olefins has been achieved through asymmetric SOMO-catalysis. A radical-polar crossover mechanism is proposed wherein olefin addition to a transient enamine radical cation and oxidation of the resulting radical furnishes a cation which is vulnerable to nucleophilic addition. A range of aromatic aldehydes a...
متن کاملEnantioselective organocatalysis using SOMO activation.
The asymmetric alpha-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, co...
متن کاملThe Intramolecular Asymmetric Allylation of Aldehydes via Organo-SOMO Catalysis: A Novel Approach to Ring Construction.
The intramolecular asymmetric cyclization of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Selective oxidation of chiral enamines (formed by the condensation of an aldehyde and a secondary amine catalyst) leads to the formation of a 3π-electron radical species. These chiral SOMO-activated radical cations undergo enantioselective cyclization with an ar...
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ژورنال
عنوان ژورنال: Angewandte Chemie International Edition
سال: 2010
ISSN: 1433-7851
DOI: 10.1002/anie.201001673