Convergent Total Synthesis of Paecilomycin B and 6′-epi-Paecilomycin B by a Barbier-Type Reaction Using 2,4,6-Triisopropylphenyllithium

被引：7

作者：

Ohba, Kiyomi ^{[1
]}

Nakata, Masaya ^{[2
]}

机构：

[1] Mitsubishi Tanabe Pharma Corp, Innovat Med Sci, Res Unit, Aoba ku, 1000 Kamoshida Cho, Yokohama, Kanagawa 2270033, Japan

[2] Keio Univ, Fac Sci & Technol, Dept Appl Chem, Kohoku Ku, 3-14-1 Hiyoshi, Yokohama, Kanagawa 2238522, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 13期

关键词：

RESORCYLIC ACID LACTONES; STEREOSELECTIVE TOTAL-SYNTHESIS; ASYMMETRIC TOTAL-SYNTHESIS; NUCLEOPHILIC ADDITIONS; C-GLYCOSIDES; STEREOSPECIFIC SYNTHESIS; 6'-EPI-COCHLIOMYCIN C; EFFICIENT SYNTHESIS; COCHLIOMYCIN C; SP SC0924;

D O I：

10.1021/acs.joc.7b03041

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The convergent total synthesis of the natural product paecilomycin B and its 6'-epimer was investigated. The aryl C-glycoside skeleton was constructed by an intramolecular Barbier-type reaction using 2,4,6-triisopropylphenyllithium and subsequent deoxygenation of the resulting anomeric hydroxy group. Starting from aryl iodide 24, the addition reaction afforded the thermodynamically stable C-beta macrocyclic adduct 41a in 29% yield and the C-alpha adduct 41b in 1% yield. Meanwhile, aryl iodide 43 (6'-epimer of 24) gave only the C-alpha adduct 44 in 76% yield. The stereoselectivities of these nucleophilic addition reactions are also discussed.

引用

页码：7019 / 7032

页数：14

共 61 条

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