Migratory hydroamination: a facile enantioselective synthesis of benzomorphans.
We describe a highly efficient, general strategy for the enantioselective synthesis of benzomorphans (45-46% overall yield from commercially available material). The new synthesis demonstrates the effectiveness of an unprecedented diastereoselective cycloisomerization via migratory hydroamination and the power of palladium-catalyzed asymmetric allylic alkylation (AAA) of simple ketone enolates in the context of complex synthesis. The strategy outlined here for the enantioselective synthesis of three contiguous stereogenic centers and the novel cycloisomerization should have many applications in alkaloid synthesis.
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Tang
Weiping
W
D000586:Amination; D000701:Analgesics, Opioid / Q000138:chemical synthesis; D001575:Benzomorphans / Q000138:chemical synthesis*; D009019:Morphinans / Q000138:chemical synthesis; D010423:Pentazocine / Q000138:chemical synthesis; D013237:Stereoisomerism
D000701:Analgesics, Opioid; D001575:Benzomorphans; D009019:Morphinans; D010423:Pentazocine; C047238:metazocine