Theoretical and Experimental Studies of a Charge-Transfer Mechanism for Biomimetic Oxygenations of Phenol and Indol Derivatives
作者： Yasunori Yoshioka , Syusuke Yamanaka , Satoru Yamada , Takashi Kawakami , Masamichi Nishino
DOI: 10.1246/BCSJ.69.2701
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摘要: The structures and stabilities of organodioxide anions, charge-transfer (CT) complexes between carbanions molecular oxygen, related solvated clusters were investigated using ab initio semiempirical MO plus intermolecular CT theories. computational results, together with experimental evidence, have revealed the characteristics potential curves, indicating that nonradical mechanism via is operative for base-catalyzed dioxygenation reactions phenol indole derivatives. following conclusions drawn from present calculations: (1) carbanion triplet oxygen proceed through a one-electron transfer (ET) to 3O2. (2) base-promoted monoanion reacts two different mechanism: one mechanism, where complex formed spin inversion singlet occurs in aprotic solvents; other involves ET assi...
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