Designed Iron Catalysts for Allylic C-H Functionalization of Propylene and Simple Olefins.
Designed Iron Catalysts for Allylic C-H Functionalization of Propylene and Simple Olefins.
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设计用于丙烯和简单烯烃的烯丙基 C-H 官能化的铁催化剂。
DOI：
10.1002/anie.202216309
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Wang,Yi-Ming
中科院分区：
文献类型：
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作者：
Wang,Ruihan;Wang,Yidong;Ding,Ruiqi;Staub,ParkerB;Zhao,ChristopherZ;Liu,Peng;Wang,Yi-Ming
全球每年通过蒸汽裂解以百万吨规模生产丙烯气体。它是一种有价值的π键官能化的起始材料，但很少用于过渡金属催化的烯丙基C-H官能化，用于精细化学合成。在此，我们报告了一种新开发的阳离子环戊二烯基二羰基铁配合物可以在催化条件下将丙烯转化为其烯丙位C-C键偶联产物。该方法也被发现适用于具有独特的支化选择性的简单α-烯烃的烯丙基官能化。实验和计算机理研究支持金属配位烯烃的烯丙基去质子化作为周转限制步骤，并导致深入了解新设计的配体在促进烯丙基C-H官能化中的多方面作用，增强了反应性和立体选择性。
Propylene gas is produced worldwide by steam cracking on million‐metric‐ton scale per year. It serves as a valuable starting material for π‐bond functionalization but is rarely applied in transition metal‐catalyzed allylic C−H functionalization for fine chemical synthesis. Herein, we report that a newly‐developed cationic cyclopentadienyliron dicarbonyl complex allows for the conversion of propylene to its allylic C−C bond coupling products under catalytic conditions. This approach was also found applicable to the allylic functionalization of simple α‐olefins with distinctive branched selectivity. Experimental and computational mechanistic studies supported the allylic deprotonation of the metal‐coordinated alkene as the turnover‐limiting step and led to insights into the multifaceted roles of the newly designed ligand in promoting allylic C−H functionalization with enhanced reactivity and stereoselectivity.