Abstract

A combined synthetic and computational (DFT) study has been performed to account for the divergent reactivity of indole-tethered ynones when treated with Ag(I) and Au(I) catalysts. The two catalyst systems deliver spirocyclic indolenines and carbazoles, respectively, from the same precursors, with the reaction outcomes believed to be a result of differences in the rates of a key protodemetalation step. A ring-opening/ring-closing isomerisation process is proposed to enable the interconversion of spirocyclic and C-2 annulated indole intermediates, in contrast to the 1,2-migration mechanism tentatively proposed in previous studies.

A combined synthetic and computational (DFT) study has been performed to account for the divergent reactivity of indole-tethered ynones when treated with Ag(I) and Au(I) catalysts. The two catalyst systems deliver spirocyclic indolenines and carbazoles, respectively, from the same precursors, with the reaction outcomes believed to be a result of differences in the rates of a key protodemetalation step. A ring-opening/ring-closing isomerisation process is proposed to enable the interconversion of spirocyclic and C-2 annulated indole intermediates, in contrast to the 1,2-migration mechanism tentatively proposed in previous studies.

中文翻译：

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吲哚链式壬烯与银（I）和金（I）催化剂的不同反应性：合成与计算研究相结合

摘要

进行了合成和计算（DFT）的组合研究，以说明用Ag（I）和Au（I）催化剂处理时，吲哚系链的炔酮的发散反应性。两种催化剂体系分别从相同的前体中释放出螺环吲哚和咔唑，其反应结果被认为是关键的原金属化步骤速率不同的结果。提出了开环/闭环异构化方法，以使螺环和C-2环氧基吲哚中间体能够相互转化，这与先前研究中暂时提出的1,2-迁移机理相反。

进行了合成和计算（DFT）的组合研究，以说明用Ag（I）和Au（I）催化剂处理时，吲哚系链的炔酮的发散反应性。两种催化剂体系分别从相同的前体中释放出螺环吲哚和咔唑，其反应结果被认为是关键的原金属化步骤速率不同的结果。提出了开环/闭环异构化方法，以使螺环和C-2环氧基吲哚中间体能够相互转化，这与先前研究中暂时提出的1,2-迁移机理相反。