Total synthesis of (+)-scyphostatin featuring an enantioselective and highly efficient route to the side-chain via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA).
(+)-Scyphostatin (1) was synthesized via (i) construction of a side-chain 3b of > or = 98% purity in 19% yield in eleven steps featuring ZACA reaction, Negishi coupling, and HWE olefination, (ii) an asymmetric synthesis of a fully protected core 4 from 10a, and (iii) a three-step assembly of 1 in 42% yield.
Laboratory of Natural Products Synthesis & Bioorganic Chemistry, Institute of Physical Chemistry, NCSR DEMOKRITOS, P.O. Box 60228, GR 153 10, Aghia Paraskevi, Greece. pitsinos@chem.demokritos.gr
Emmanuel
E
Pitsinos
Nikolaos
N
Athinaios
Zhaoqing
Z
Xu
Guangwei
G
Wang
Ei-ichi
E
Negishi
D000475:Alkenes / Q000737:chemistry*; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D011753:Pyrones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D015040:Zirconium / Q000737:chemistry*
D000475:Alkenes; D000577:Amides; D011753:Pyrones; C121123:scyphostatin; D015040:Zirconium