Total Synthesis of (−)-Batrachotoxinin A: A Local-Desymmetrization Approach

An enantioselective total synthesis of (−)-batrachotoxinin A is accomplished based on a key photoredox coupling reaction and the subsequent local-desymmetrization operation. After the expedient assembly of the highly oxidized steroid skeleton, a delicate sequence of redox manipulations was carried out to deliver a late-stage intermediate on gram scale—and ultimately (−)-batrachotoxinin A in an efficient manner.