Rh-Catalyzed Cascade C-C/Colefin-H Activations and Mechanistic Insight

被引：19
作者：
Wang, Yuxi [1 ,2 ,3 ]
Qiu, Bo [1 ,2 ,3 ]
Hu, Lingfei [4 ]
Lu, Gang [4 ]
Xu, Tao [1 ,2 ,3 ]
机构：
[1] Ocean Univ China, Sch Med & Pharm, Mol Synth Ctr, Qingdao 266003, Peoples R China
[2] Ocean Univ China, Sch Med & Pharm, Key Lab Marine Drugs, Minist Educ, Qingdao 266003, Peoples R China
[3] Pilot NLMST, Lab Marine Drugs & Bioprod & Open Studio Druggabi, Qingdao 266237, Peoples R China
[4] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Peoples R China
来源：
ACS CATALYSIS | 2021年 / 11卷 / 15期
关键词：
C-C activation; C-H activation; reverse concerted metalation-deprotonation (reverse CMD); Rh catalysis; interrupted "cut and sew; cascade C-C/C-H; BOND ACTIVATION; CLEAVAGE; CARBOACYLATION; ACCESS; RHODACYCLOPENTANONES;
D O I：
10.1021/acscatal.1c02480
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A reverse concerted metalation-deprotonation (CMD) process has been proposed as a key step to rationalize our newly discovered Rh-catalyzed C-C/Colefin-H cascade reaction to access 1-benzazepines. The reaction features redox-neutral conditions with 100% atom economy and showed broad substrate scope and good efficiency (23 examples, up to 85% yield). DFT calculations indicated that the reverse CMD process is a key step to kinetically override the normal "cut and sew" process and rendered the sequential olefinic C-H activation/reductive elimination as the predominant pathway.
引用
收藏
页码：9136 / 9142
页数：7
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