Journal of Organic Chemistry p. 2224 - 2229 (1980)
Update date:2022-08-03
Topics:
Ronald, Robert C.
Gewali, Mohan B.
Ronald, Bruce P.
The total synthesis of optically active (-)-aplysin (1) and (-)-debromoaplysin (2) employing novel (isopinocampheyloxy)methyl ethers for phenolic hydroxyl protection and diastereomeric resolution is described.A key transformation is the unusual cyclization of the diastereomeric chlorohydrins 12 and 13 in methanolic base to form the enantiomeric tricyclic alcohols (-)-16 and (+)-16 with cleavage of the acetal-linked (isopinocampheyloxy)methyl resolving/protecting group.This transformation was followed by substitution of the tertiary hydroxyl via the derived chloride with a methyl group by Grignard coupling with methylmagnesium bromide.The methyl insertion occurred with retention of configuration and resulted in formation of the natural aplysin system from 12 in just three steps.The conversion of the methylated tricyclic ether 20 to (-)-debromoaplysin (2) was accomplished in two steps by double bond isomerization and selective reduction.Bromination of (-)-2 afforded (-)-aplysin (1).
View MoreContact:+(852) 301-98033
Address:Flat C, 23/F, Lucky Plaza, 315-321 Lockhart Road, Wan Chai, Hong Kong
Jiande City Silibase Silicone New Material Manufacture Co., Ltd.
Contact:15967177856
Address:Genglou Industrial Development Area
Hangzhou Yingshanhua Pigment Chemicals Co.,Ltd.
Contact:+86-0150-58101658
Address:Nanyang Economic DevelopmentZong,Xiaoshan,Hangzhou,China
Yueyang Hudex Pharmaceuticals Ltd.
Contact:0730-8748800
Address:Wujiang Bridge,Yueyang Economy & Technology Development Zone
Contact:86-379-63338609
Address:Jiudian Village,Deting Town,Song County,Luoyang
Doi:10.1021/jo01299a007
(1980)Doi:10.1021/jo01300a053
(1980)Doi:10.1021/op060128m
(2006)Doi:10.1021/jo01301a031
(1980)Doi:10.1016/S0040-4039(01)87724-8
(1969)Doi:10.1007/BF02151788
(1964)