The Doyle–Kirmse reaction represents a powerful synthetic tool for forming both C–S
and C–C bonds in a single process. The rhodium-catalyzed Doyle–Kirmse reaction of
S-allyl and S-propargyl phosphorothioates with diazoesters has been developed and represents a
rare example involving substrates bearing an electron-withdrawing group on the sulfur
atom. The transformation takes place at room temperature, in only 5 minutes, and leads
via a [2,3]-sigmatropic rearrangement of the sulfonium ylide intermediate to the corresponding
S-homoallyl or S-homoallenyl phosphorothioates in yields ranging from 25% to 92% (19 examples).
Key words
Doyle–Kirmse reaction - [2,3]-rearrangement - propargyl sulfides - allyl sulfides
- diazoesters - phosphorothioates - C–S bond formation
