Enantioselective Total Synthesis of Pinnaic Acid and Halichlorine

被引：29

作者：

Xu, Shu ^{[1
]}

Unabara, Daisuke ^{[1
]}

Uemura, Daisuke ^{[2
]}

Arimoto, Hirokazu ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Life Sci, Sendai, Miyagi 9808577, Japan

[2] Kanagawa Univ, Dept Chem, Fac Sci, Hiratsuka, Kanagawa 2591293, Japan

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2014年 / 9卷 / 01期

关键词：

cyclization; metathesis; natural products; stereoselectivity; total synthesis; COMBINING 2-DIRECTIONAL SYNTHESIS; SPIROCYCLIC CORE; TRICYCLIC CORE; ASYMMETRIC CONSTRUCTION; AZASPIROCYCLIC CORE; RADICAL CYCLIZATION; CLOSING METATHESIS; (+/-)-PINNAIC ACID; FORMAL SYNTHESIS; TANDEM REACTIONS;

D O I：

10.1002/asia.201301248

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The enantioselective total synthesis of the bioactive marine natural products pinnaic acid and halichlorine is reported in detail. Our total synthesis features the construction of the five-membered ring and C9 and C13 stereogenic centers through a palladium-catalyzed trimethylenemethane [3+2] cyclization; the installation of the nitrogen atom through a regioselective Beckmann rearrangement of a poorly reactive ketone; the stereoselective cyclization of the spiro ring through a four-step, one-pot hydrogenation-cyclization; and efficient connection of the sterically hindered lower chain through a reduced-pressure cross olefin metathesis reaction.

引用

页码：367 / 375

页数：9