Convergency and divergency as strategic elements in total synthesis: the total synthesis of (-)-drupacine and the formal total synthesis of (+/-)-cephalotaxine, (-)-cephalotaxine, and (+)-cephalotaxine.
A concise route toward the syntheses of (-)-drupacine and (+)- and (-)-cephalotaxine has been developed. The syntheses rely on Pd(II)-catalyzed aerobic oxidative heterocyclization chemistry, which was employed to rapidly construct an important spirocyclic amine intermediate. A dynamic beta-elimination/conjugate addition process was strategically applied to complete the first asymmetric total synthesis of (-)-drupacine.
Liu
Qi
Q
The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Ferreira
Eric M
EM
Stoltz
Brian M
BM
D002384:Catalysis; D003500:Cyclization; D006248:Harringtonines / Q000138:chemical synthesis*; D000077863:Homoharringtonine; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
D006248:Harringtonines; C007562:drupacine; D010165:Palladium; D000077863:Homoharringtonine