Abstract
During our efforts toward the synthesis of naturally occurring polyprenylated polycyclic acylphloroglucinol using a AuI-catalyzed 6-endo dig carbocyclization, we isolated stable vinyllic gold intermediates. Optimization lead to isolated yields of up to 98%, using 2-(di-tert-butyl-phosphino)biphenyl as the ligand. This transformation is derived from a silyl rearrangement that can be fully controlled according to the nature of the substituent on the ynone. This selective transformation does not require basic conditions to prevent protodeauration. These vinyl-gold complexes are the first isolated intermediates during a silyl migration with gold(I). More than 16 new organo-gold complexes were synthesized and characterized by single-crystal X-ray diffraction. Reactivity of these complexes is also presented.