Anti-Markovnikov stereoselective hydroamination and hydrothiolation of (hetero)aromatic alkynes using a metal-free cyclic trimeric phosphazene base

• Published in: Tetrahedron Vol. 75; no. 25; pp. 3432 - 3440
• Main Authors: Zhao, Na, Lin, Chengdong, Wen, Lirong, Li, Zhibo
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 21-06-2019
• Subjects: Cyclic trimeric phosphazene base; Hydroamination; Hydrothiolation; Organocatalysis; Hydrothiolation; Hydroamination; Organocatalysis; Cyclic trimeric phosphazene base
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2019.04.075

Hydroamination and hydrothiolation are the most efficient and completely atom-economical process to construct important enamine and vinyl sulfide intermediates in pharmaceutical and organic chemistry. The cyclic trimeric phosphazene base (CTPB) showed great catalytic activity for the anti-Markovnikov stereoselective hydroamination and hydrothiolation of alkynes in good to excellent yields. A broad substrate scope of alkynes and nucleophiles was demonstrated, including aryl and heteroaryl alkynes, terminal and internal alkynes, different N-heterocycles, thiols and thiophenols. This versatile and cost-efficient approach with good stereoselectivity and excellent functional group tolerance provided new opportunity for the organocatalyzed hydrofunctionalization of alkynes.
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