Stille Coupling Overview: Organostannanes with Halides

Abstract

Stille coupling reaction, named after its pioneer John K. Stille, involves the coupling of an organic electrophile with an organostannane compound in the presence of an active Pd(0) species to form a coupled product comprising both coupling partners.

The organic electrophiles are aryl, or vinyl halides (I, Br, Cl), or triflates (OTf). The nucleophilic partners are organostannane compounds comprising the metal at the center, bonded to three identical alkyl (tributyl- or trimethyl-) groups and one distinct coupling partner—an aryl, vinyl, or a benzyl group. Most organostannane compounds are commercially available; however, they can also be readily synthesized by reacting tributyl chloride with Grignard reagents.

Stille coupling can be used to join two aromatic systems to generate biaryl systems.

Similarly, using aryl and vinyl coupling partners, styrene derivatives can be generated.

Stille coupling is also used to prepare conjugated dienes. The reactions are observed to be stereospecific with retention of configuration at each C–C double bond.

Coupling an aryl with a benzyl group forms a new bond with sp²- and sp³- carbon centers.

Further, some of the applications of Stille coupling are observed towards the synthesis of aldehydes and ketones.