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pubmed-article:19639997pubmed:abstractTextThe intramolecular alpha-arylation 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 3pi-electron radical species. These chiral SOMO-activated radical cations undergo enantioselective reaction with an array of pendent electron-rich aromatics and heterocycles thus efficiently providing cyclic alpha-aryl aldehyde products (10 examples: > or = 70% yield and > or = 90% ee). In accordance with our radical mechanism, when there is a choice between arylation at the ortho or para position of anisole substrates, we find that arylation proceeds selectively at the ortho position.lld:pubmed
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pubmed-article:19639997pubmed:authorpubmed-author:ConradJay CJClld:pubmed
pubmed-article:19639997pubmed:authorpubmed-author:KongJongrockJlld:pubmed
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pubmed-article:19639997pubmed:pagination11640-1lld:pubmed
pubmed-article:19639997pubmed:dateRevised2010-9-27lld:pubmed
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pubmed-article:19639997pubmed:articleTitleEnantioselective alpha-arylation of aldehydes via organo-SOMO catalysis. An ortho-selective arylation reaction based on an open-shell pathway.lld:pubmed
pubmed-article:19639997pubmed:affiliationMerck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, USA.lld:pubmed
pubmed-article:19639997pubmed:publicationTypeJournal Articlelld:pubmed
pubmed-article:19639997pubmed:publicationTypeResearch Support, Non-U.S. Gov'tlld:pubmed
pubmed-article:19639997pubmed:publicationTypeResearch Support, N.I.H., Extramurallld:pubmed
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