SYNTHETIC APPROACHES TO THE AXANE FAMILY OF SESQUITERPENOIDS - TOTAL SYNTHESIS OF DL-AXAMIDE-4, DL-AXISONITRILE-4, AND DL-AXISOTHIOCYANATE-4

被引:31
作者
CHENERA, B [1 ]
CHUANG, CP [1 ]
HART, DJ [1 ]
LAI, CS [1 ]
机构
[1] OHIO STATE UNIV, DEPT CHEM, 120 W 18TH AVE, COLUMBUS, OH 43210 USA
关键词
D O I
10.1021/jo00033a023
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Two methods for the preparation of perhydroindan 7 are described. One involves an intramolecular free radical cyclization in a key step and proceeds in 13 steps and 9% yield from anisole (9). The other involves an intramolecular conjugate addition mediated by pyrrolidine (28 --> 7) and proceeds in five steps and 30% overall yield from vinylogous ester 29. Two unsuccessful attempts to convert 7 into axane sesquiterpenoids 1-6 are described. The synthesis of axanes 4-6 was achieved using a potassium tert-butoxide catalyzed cyclization of a dienoic keto ester as a key step (47 + 48 --> 49). Conversion of alpha,beta-unsaturated ester 49 to vinyl isocyanate 57 was accomplished using a Curtius rearrangement and reduction of 57 with lithium triethylborohydride completed the synthesis of axamide-4 (4). The preparation of axisonitrile-4 (5) and axisothiocyanate-4 (6) from 4 is also described.
引用
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页码:2018 / 2029
页数:12
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