Synthesis ( IF 2.2 ) Pub Date : 2018-07-04 , DOI: 10.1055/s-0037-1610181 Jason Lynam , Richard Taylor , William Unsworth , John Liddon , James Rossi-Ashton , Aimee Clarke
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:
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。