We have developed a DPPE-catalyzed three molecular two component tandem reaction of γ-substituted allenoate and CS2 to construct 2-thineyl vinyl sulfide through phosphine catalyzed [3+2] cyclization followed by Michael addition. The synthetic value of the 2-thineyl vinyl sulfide was demonstrated by a concise synthesis of an anti-glaucoma agent.
![Graphical abstract: Phosphine catalyzed [3+2] cyclization/Michael addition of allenoate with CS2 to form 2-thineyl vinyl sulfide](http://hg.y866.cn/compound/lib/scimg/usr/1/D0CC05070A.jpg)
