GENERAL-APPROACH TO HALOGENATED TETRAHYDROFURAN NATURAL-PRODUCTS FROM RED ALGAE OF THE GENUS LAURENCIA - TOTAL SYNTHESIS OF (+/-)-KUMAUSALLENE AND (+/-)-1-EPI-KUMAUSALLENE

被引:107
作者
GRESE, TA [1 ]
HUTCHINSON, KD [1 ]
OVERMAN, LE [1 ]
机构
[1] UNIV CALIF IRVINE,DEPT CHEM,IRVINE,CA 92717
关键词
D O I
10.1021/jo00061a021
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.
引用
收藏
页码:2468 / 2477
页数:10
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