Enantioselective Total Synthesis of (+)-Hinckdentine A via a Catalytic Dearomatization Approach

被引：120

作者：

Douki, Kazuya ^{[1
]}

Ono, Hiroyuki ^{[2
]}

Taniguchi, Tohru ^{[3
]}

Shimokawa, Jun ^{[1
]}

Kitamura, Masato ^{[1
]}

Fukuyama, Tohru ^{[1
]}

机构：

[1] Nagoya Univ, Grad Sch Pharmaceut Sci, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648601, Japan

[2] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1130033, Japan

[3] Hokkaido Univ, Frontier Res Ctr Postgenome Sci & Technol, Fac Adv Life Sci, Kita 21 Nishi 11, Sapporo, Hokkaido 0010021, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 44期

基金：

日本科学技术振兴机构;

关键词：

DENSITY-FUNCTIONAL THEORY; ASYMMETRIC DEAROMATIZATION; ARYLATIVE DEAROMATIZATION; ABSOLUTE-CONFIGURATION; PHENOL DEAROMATIZATION; DERIVATIVES; INDOLES; ISOTHIOCYANATES; CONSTRUCTION; HINCKDENTINE;

D O I：

10.1021/jacs.6b10237

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Optically pure hinckdentine A was synthesized on a 300 mg scale via an asymmetric catalysis-based strategy. The key steps to the first asymmetric synthesis involved (i) enantioselective dearomative cyclization of an achiral N-acyl indole that allowed for the efficient construction of the key polycyclic indoline intermediate with a crucial tetrasubstituted stereogenic carbon center, (ii) Beckmann fragmentation-mediated ring expansion, (iii) rearrangement-based introduction of an anilinic nitrogen atom, (iv) regioselective tribromination, and (v) final closure of the cyclic amidine moiety.

引用

页码：14578 / 14581

页数：4

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