Cascade C−H Activation and Two C−C Bond Forming in Reaction of Azalutetacyclopentadiene with 2‐Methylbenzonitriles

Author:

Chai Zhengqi1,Lv Ze‐Jie1,Liu Wei1,Yang Jinxiao1,Wei Junnian1,Zhang Wen‐Xiong1ORCID

Affiliation:

1. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering Peking University Beijing 100871 P. R. China

Abstract

AbstractAzametallacyclopentadienes are an important class of metallacycles as the key intermediates in metal‐promoted or catalyzed carbon‐carbon coupling reaction of nitriles and alkynes. Rare‐earth azametallacyclopentadienes have shown various reactivity toward nitriles, depending on the substituents of nitriles. The reaction of azalutetacyclopentadienes toward 2‐methylbenzonitriles has been investigated in this work, which selectively affords the fused 7‐5‐6‐membered azalutetacycles as products. Computational studies reveal that the reaction of azalutetacyclopentadienes toward 2‐methylbenzonitriles selectively initiates with the remote activation of the benzylic C−H bond by the Lu−N bond, followed by the intramolecular nucleophilic attack from the deprotonated benzylic carbon to form a C−C bond. Subsequently, the high ring strain promoted the generation of the uncoordinated carbanion dissociated from the lutetium center, which then undergoes intramolecular nucleophilic attack toward C=N triple bond to give the final product containing fused 7‐5‐6‐membered azalutetacycle. This work not only achieves highly selective three‐step cascade reaction to form a unique class of rare‐earth metallacycle, but also provides a new idea for the transformation of unsaturated substrates with C−H bonds that can be activated.

Publisher

Wiley

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3