Stereoselective synthesis of deoxy analogues of the 3C-protease inhibitor thysanone
Stereoselective synthesis of deoxy analogues of the 3C-protease inhibitor thysanone
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DOI：
10.1016/s0040-4020(01)01120-6
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发表时间：
2002-01-01
期刊：
影响因子：
2.1
通讯作者：
Elliott, RJR
中科院分区：
文献类型：
--
作者：
Brimble, MA;Elliott, RJR
以烯丙萘5为起始原料，经环氧化还原为溴醇7，合成了外消旋7,9-二脱氧thyysanone 9。随后溴化物的锂化和DMF的猝灭使乳酸菌8经过干净的氧化去甲基化成为外消旋的6,8-二脱氧囊氨酮9。从(R)-环氧化物6开始，通过烯丙萘5的Sharpless不对称二羟基化反应合成(1R,3S)-(+)-7,9-二脱氧异构体酮9，尽管在低ee下得到。以(R)-溴醇7为起始原料，采用手性恶唑硼烷对酮12进行不对称还原，得到(IS,3R)-(+)-7,9-二脱氧thyanone 9。以烯丙基萘5为原料，采用瓦克氧化法制备了关键酮12。(C) 2002 Elsevier Science Ltd.版权所有。
The synthesis of racemic 7,9-dideoxythysanone 9 was achieved starting from allyinaphthalene 5 via epoxidation and reduction to bromoalcohol 7. Subsequent lithiation of the bromide and quenching with DMF afforded lactol 8 which underwent clean oxidative demethylation to racemic 6,8-dideoxythysanone 9. The synthesis of (1R,3S)-(+)-7,9-dideoxythysanone 9 was then achieved albeit in low ee, starting from (R)-epoxide 6 which in turn was obtained via Sharpless asymmetric dihydroxylation of allylnaphthalene 5. An improved asymmetric synthesis of (IS,3R)-(+)-7,9-dideoxythysanone 9 in 72% ee was then accomplished starting from (R)-bromoalcohol 7 which was obtained via asymmetric reduction of ketone 12 using a modified chiral oxazaborolidine. The key ketone 12 in turn was prepared by Wacker oxidation of allylnaphthalene 5. (C) 2002 Elsevier Science Ltd. All rights reserved.