Fe(III)-Based Tandem Catalysis for Amidomethylative Multiple Substitution Reactions of α‑Substituted Styrene Derivatives

• Published in: ACS catalysis Vol. 10; no. 18; pp. 10627 - 10636
• Main Authors: Qian, Xiaolin, Zhou, Hui, Chaminda Lakmal, Hetti Handi, Lucore, James, Wang, Xuesong, Valle, Henry U, Donnadieu, Bruno, Xu, Xue, Cui, Xin
• Format: Journal Article
• Language: English
• Published: American Chemical Society 18.09.2020
• Subjects: amidomethylation; alkene substitution; Lewis acid catalysis; tandem catalysis; nitrogen heterocycles
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.0c02676

Developing tandem multiple C–H substitution reactions of simple alkenes provides rapid access to structurally complex unsaturated building blocks. Amidomethylative reactions that reserve CC double bonds have been composed sequentially for tandem catalytic substitutions around the CC bonds of alkenes. As a proof-of-concept demonstration, tandem catalytic amidomethylative processes, which effectively form multiple C–C bonds, have been developed to directly and selectively transform α-substituted styrenes into unsaturated N-heterocycles. Using Fe­(OTf)3 as the sole catalyst, the operationally simple protocols employ bench-stable bisamidomethane as the sole reagent to produce hexahydropyrimidines and 1,2,3,6-tetrahydropyridine derivatives. Moreover, the practical catalytic processes constituted facile two-step pathways, from simple α-substituted styrenes, to access unsaturated 1,3-diamine and bispidine derivatives.