Total Synthesis of (±)-Cafestol: A Late-Stage Construction of the Furan Ring Inspired by a Biosynthesis Strategy

被引：50
|
作者：
Zhu, Lili [1 ]
Luo, Jisheng [1 ]
Hong, Ran [1 ]
机构：
[1] Chinese Acad Sci, Shanghai Inst Organ Chem, CAS Key Lab Synthet Chem Nat Subst, Shanghai 200032, Peoples R China
来源：
ORGANIC LETTERS | 2014年 / 16卷 / 08期
基金：
中国国家自然科学基金;
关键词：
METAL PEROXIDE REACTIONS; CATALYZED ENE REACTIONS; ENANTIOSELECTIVE POLYENE CYCLIZATION; ABSOLUTE CONFIGURATION; KAURANE DITERPENOIDS; EUDESMANE TERPENES; ORGANIC-SYNTHESIS; CAFESTOL; ACID; KAHWEOL;
D O I：
10.1021/ol500623w
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
An efficient bioinspired approach to the total synthesis of (+/-)-cafestol features a late-stage installation of the furan ring with a mild Au-catalyzed cycloisomerization. The Et2AlCl-promoted aldehyde-ene cyclization and subsequent Friedel Crafts reaction deliver a requisite tricyclic system in gram scale with high stereo- and regioselectivity. Moreover, a highly stereoselective SmI(2)mediated aldehyde alkene radical cyclization furnishes the key bicyclo[3.2.1]octane skeleton to offer an advanced intermediate for the synthesis of other oxygenated ent-kaurene diterpenoids.
引用
收藏
页码：2162 / 2165
页数：4
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