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Theoretical Studies on Rh-Catalyzed Cycloisomerization of Homopropargylallene-Alkynes through C(sp3)–C(sp) Bond Activation
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-01-14 , DOI: 10.1021/acscatal.9b04985 Ying Ren 1, 2 , Zhenyang Lin 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-01-14 , DOI: 10.1021/acscatal.9b04985 Ying Ren 1, 2 , Zhenyang Lin 1
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A systematic theoretical study has been carried out with the aid of density functional theory (DFT) calculations on the mechanism of the Rh-catalyzed cycloisomerization of homopropargylallene-alkynes through C(sp3)–C(sp) bond activation. The DFT results indicate that the catalytic cycle is divided into four main processes involving oxidative coupling, insertion, 1,3-alkyl migration, and 1,2-alkyl migration or 1,2-H migration. It is found that a Rh(I) Fischer carbene intermediate, which is derived from the third process 1,3-alkyl migration, selectively determines the formation of the six/five/five tricycle Product 1 or the six/five/four tricycle Product 2, depending on the substitutes on the substrates. The origin of cycloisomerization product selectivity has also been addressed.
中文翻译：
通过C（sp 3）–C（sp）键活化Rh催化同炔丙基烯丙炔的环异构化的理论研究
借助密度泛函理论（DFT）计算，通过C（sp 3）–C（sp）键活化，Rho催化高炔丙炔烯炔的环异构化机理进行了系统的理论研究。DFT结果表明，催化循环分为四个主要过程，涉及氧化偶联，插入，1，3-烷基迁移和1，2-烷基迁移或1，2-H迁移。发现源自第三过程1，3-烷基迁移的Rh（I）费歇尔卡宾中间体选择性地确定六/五/五三轮车产物1或六/五/四三轮车产物的形成。 2个，取决于基材上的替代物。还解决了环异构化产物选择性的起源。
更新日期：2020-01-15
中文翻译：
通过C（sp 3）–C（sp）键活化Rh催化同炔丙基烯丙炔的环异构化的理论研究
借助密度泛函理论（DFT）计算，通过C（sp 3）–C（sp）键活化，Rho催化高炔丙炔烯炔的环异构化机理进行了系统的理论研究。DFT结果表明，催化循环分为四个主要过程，涉及氧化偶联，插入，1，3-烷基迁移和1，2-烷基迁移或1，2-H迁移。发现源自第三过程1，3-烷基迁移的Rh（I）费歇尔卡宾中间体选择性地确定六/五/五三轮车产物1或六/五/四三轮车产物的形成。 2个，取决于基材上的替代物。还解决了环异构化产物选择性的起源。
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