Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA.
School of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China.
Angew Chem Int Ed Engl. 2023 Mar 1;62(10):e202216309. doi: 10.1002/anie.202216309. Epub 2023 Jan 31.
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.
丙烯气体在全球范围内通过每年百万吨级的蒸汽裂解生产。它是π键官能化的有价值的起始原料，但很少应用于过渡金属催化的烯丙基 C-H 官能化以进行精细化学品合成。在此，我们报告了一种新开发的阳离子环戊二烯基铁二羰基配合物，允许在催化条件下将丙烯转化为其烯丙基 C-C 键偶联产物。该方法还发现适用于具有独特支链选择性的简单α-烯烃的烯丙基官能化。实验和计算的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，并深入了解了新设计配体在促进具有增强反应性和立体选择性的烯丙基 C-H 官能化中的多方面作用。
