THE CHEMISTRY OF CYCLIC VINYL ETHERS .6. TOTAL SYNTHESIS OF POLYETHER IONOPHORE ANTIBIOTICS OF THE CALCIMYCIN (A-23187) CLASS

被引:74
作者
BOECKMAN, RK
CHARETTE, AB
ASBEROM, T
JOHNSTON, BH
机构
[1] Department of Chemistry, University of Rochester, Rochester
关键词
D O I
10.1021/ja00014a029
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An extremely convergent (longest linear sequence, 16 steps), fully stereoselective, and potentially general synthesis of the antibiotic ionophores of the Calcimycin (A-23187) class was devised. The key steps involve a coupling reaction between the chiral nonracemic subunits dihydropyran 41 (as the alpha-lithio anion) and bromide 49. Subsequent acid-promoted cyclization directly produces the spirocyclic ring system found in the ionophore X-14885A (3). Alternatively, cyclopropanation of substituted vinyl ether 55 followed by acid treatment afforded the spiroketal 58 that was subsequently converted into the polyether ionophore Calcimycin (1) and also Cezomycin (2).
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页码:5337 / 5353
页数:17
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