Synthesis of the 1,2-seco fusicoccane diterpene skeleton by Stille coupling reaction between the highly functionalized A and C ring segments of cotylenin A

被引：8

作者：

Kuwata, Kazuaki ^{[1
]}

Hanaya, Kengo ^{[1
]}

Higashibayashi, Shuhei ^{[1
]}

Sugai, Takeshi ^{[1
]}

Shoji, Mitsuru ^{[1
,2
]}

机构：

[1] Keio Univ, Dept Pharmaceut Sci, Fac Pharm, Minato Ku, 1-5-30 Shibakoen, Tokyo 1058512, Japan

[2] Yokohama Univ Pharm, Fac Pharm, 601 Matano Cho, Yokohama, Kanagawa 2450066, Japan

来源：

TETRAHEDRON | 2017年 / 73卷 / 41期

关键词：

Natural product synthesis; Cyclic terpenoid; Seco-fusicoccane skeleton; Stille coupling; Alkenylstannane; Alkenyl triflate; PEPPSI-SIPr; STEREOSELECTIVE-SYNTHESIS; ENE REACTION; GROWTH; DIFFERENTIATION; CONFIRMATION; TERPENOIDS; CARCINOMA; CATALYST; ALPHA; CELLS;

D O I：

10.1016/j.tet.2017.08.056

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

1-Hydroxy-14-isopropy1-3 beta-methoxymethy1-7 beta,11 beta-dimethyl-3 alpha-[((2-trimethylsily1)ethoxy)methoxyl1,2-secofusicocca-8,10(14)-dien-2-one, a highly functionalized 1,2-seco fusicoccane diterpene skeleton related to cotylenin A was synthesized in a convergent manner. The A ring segment, i.e., (1'R,2S, 2'E,5S)-2-methoxymethy1-5-[1'-methyl-3'-(trimethylstannyl)prop-2-eny1]-2-[((2 ''-trimethylsilyl)ethoxy) methoxy]cyclopentanone, was synthesized in 20.1% yield over 18 steps from known (S)-5-isopropenyl-2methylcyclopent-1-enecarbaldehyde. This was coupled with the C ring segment, i. e., (R)-5-hydroxymethy1-2-isopropy1-5-methylcyclopent-1-en-1-y1 trifluoromethylsulfonate, which was prepared according to our previous report. The Stille coupling reaction between alkenylstannane and sterically hindered triflate proceeded successfully in the presence of PEPPSI-SIPr (85%), and the total yield of the target molecule was 17.1% over the longest linear sequences (19 steps) from (S)-5-isopropeny1-2methylcyclopent-1-enecarbaldehyde. (C) 2017 Elsevier Ltd. All rights reserved.

引用

页码：6039 / 6045

页数：7

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