Carbopalladation Cascades – Not only syn, but also anti

Seminar | March 4 | 1:30-2:30 p.m. | 775B Tan Hall

 Prof. Daniel Werz, Technical University Braunschweig

 College of Chemistry

A characteristic feature of carbopalladation reactions is the syn-attack of the organopalladium species LnX[Pd]-R on the reacting π-system. Such a step results in compounds bearing Pd and R on the same side of the originating alkene moiety. Embedded into longer domino sequences complex structures are efficiently obtained by a repetition of this syn-carbopalladation step. In this way, linear oligoynes were cyclized in a dumbbell-mode and led to benzene-type structures or higher oligoenes. We exploited this chemistry to synthesize not only chromans, isochromans and dibenzopentafulvalenes, but also to access the most truncated π-helicenes which only consist of a Z,Z,Z,..-oligoene chain that is fixed in an all s-cis arrangement. All these domino processes are based on a syn-carbopalladation cascade. However, a carbopalladation cascade involving formal anti-carbopalladation steps opens new avenues to create compounds with tetrasubstituted double bonds. Such a process was realized, and mechanistically and computationally investigated. The synthetic potential was demonstrated for the preparation of various oligocyclic frameworks (including natural products) by making use of a variety of different terminating processes.

 debgray@berkeley.edu

 Carbopalladation Cascades – Not only syn, but also anti