1,4-Pentenyne as a five-carbon synthon for efficient and selective syntheses of natural products containing 2,4-dimethyl-1-penten-1,5-ylidene and related moieties by means of Zr-catalyzed carboalumination of alkynes and alkenes.
Two highly efficient protocols for enantioselective synthesis of 2,4-dimethyl-1-penten-1,5-ylidene derivatives involve the combined use of the Zr-catalyzed methylalumination of alkynes (ZMA) and the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA). The ZMA/ZACA protocol has been applied to the synthesis of a nafuredin intermediate 14 and a potential intermediate 18 for milbemycin beta 3, while the ZACA/ZMA protocol has been applied to the synthesis of a (-)-bafilomycin A(1) intermediate 25.
Zhu
Gangguo
G
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084, USA.
Negishi
Ei-ichi
E
D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D017607:Aluminum Compounds / Q000737:chemistry*; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D008049:Lipase / Q000378:metabolism; D015394:Molecular Structure; D011753:Pyrones / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry*
D000475:Alkenes; D000480:Alkynes; D017607:Aluminum Compounds; D001688:Biological Products; D011753:Pyrones; C423563:nafuredin; D002244:Carbon; D015040:Zirconium; D008049:Lipase