ABSTRACT
The power of Rh-mediated intramolecular C -H insertion can be seen in the cyclization of the a-diazo ester 1 (Scheme 1). Although four diastereomers could have been formed from this cyclization, only 2, the key intermediate for the synthesis of the dendrobatid alkaloid 25IF 3, was in fact observed. This outcome, as ex plained in detail shortly, had first been predicted computationally. This chapter summarizes our computational approach toward understanding the transition state (“ point of commitment” ) for these Rh-mediated cyclizations. As we discuss at the end of this chapter, there is yet much left to be learned.
