转鼓
化学
激进的
光催化
脱羧
光化学
自由基离子
电子受体
组合化学
有机化学
离子
催化作用
亲核细胞
作者
Tobias Morack,Christian Mück‐Lichtenfeld,Ryan Gilmour
标识
DOI:10.1002/anie.201809601
摘要
A bioinspired, intermolecular radical Stetter reaction of α-keto acids and aldehydes is disclosed that is contingent on a formal "radical umpolung" concept. Enabled by secondary amine activation, electrostatic recognition ensures that the α-ketocarboxylic acids, which function as latent acyl radicals, are proximal to the in situ generated iminium salts. This photoactive contact ion pair is an electron donor-acceptor (EDA) complex, and undergoes facile single electron transfer (SET) and rapid decarboxylation prior to radical-radical recombination. Importantly, decarbonylation is mitigated by this strategy. The initial computational validation on which the process is predicated matches closely with experiment. Synergising organo- and photocatalysis activation principles finally expands the mechanistic and synthetic scope of the classic Stetter reaction to include α,β-unsaturated aldehydes as acceptors.
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