Formal Synthesis of Gracilamine Using Rh(I)-Catalyzed [3 + 2 + 1] Cycloaddition of 1-Yne-Vinylcyclopropanes and CO.
Reported here is a formal synthesis of gracilamine using Rh(I)-catalyzed [3 + 2 + 1] reaction of yne-VCP (±)-4 and CO. The key reaction gave the cycloadduct (±)-trans-3 with the A-B-C core structure of gracilamine. This advanced intermediate was further transformed to Gao's intermediate (±)-2 via regular transformations to realize the formal synthesis of gracilamine. The present strategy was used to accomplish the asymmetric formal synthesis of gracilamine using chiral substrate (+)-4.
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
Sritama
S
Bose
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
Jun
J
Yang
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
Zhi-Xiang
ZX
Yu
D047151:Amaryllidaceae Alkaloids / Q000138:chemical synthesis*; D002384:Catalysis; D003500:Cyclization; D061565:Cycloaddition Reaction; D003521:Cyclopropanes / Q000737:chemistry*; D027801:Galanthus / Q000737:chemistry; D008968:Molecular Conformation; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry
D047151:Amaryllidaceae Alkaloids; D003521:Cyclopropanes; D014753:Vinyl Compounds; C578306:gracilamine; D012238:Rhodium