Green oxidation of indoles using halide catalysis

被引：116

作者：

Xu, Jun ^{[1
,2
,3
]}

Liang, Lixin ^{[2
]}

Zheng, Haohao ^{[1
]}

Chi, Yonggui Robin ^{[3
]}

Tong, Rongbiao ^{[2
]}

机构：

[1] Guizhou Univ Tradit Chinese Med, Coll Pharm, Guiyang, Guizhou, Peoples R China

[2] HKUST, Dept Chem, Kowloon, Clear Water Bay, Hong Kong, Peoples R China

[3] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore

来源：

NATURE COMMUNICATIONS | 2019年 / 10卷 / 1期

基金：

中国国家自然科学基金;

关键词：

C-H; ALKALOIDS; OXINDOLE; REARRANGEMENT; CONVERSION; ROUTE; TRANSFORMATIONS; MITRAPHYLLINE; PHYSOSTIGMINE; DERIVATIVES;

D O I：

10.1038/s41467-019-12768-4

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Oxidation of indoles is a fundamental organic transformation to deliver a variety of synthetically and pharmaceutically valuable nitrogen-containing compounds. Prior methods require the use of either organic oxidants (meta-chloroperoxybenzoic acid, N-bromosuccinimide, t-BuOCl) or stoichiometric toxic transition metals [Pb(OAc)(4), OsO4, CrO3], which produced oxidant-derived by-products that are harmful to human health, pollute the environment and entail immediate purification. A general catalysis protocol using safer oxidants (H2O2, oxone, O-2) is highly desirable. Herein, we report a unified, efficient halide catalysis for three oxidation reactions of indoles using oxone as the terminal oxidant, namely oxidative rearrangement of tetrahydro-beta-carbolines, indole oxidation to 2-oxindoles, and Witkop oxidation. This halide catalysis protocol represents a general, green oxidation method and is expected to be used widely due to several advantageous aspects including waste prevention, less hazardous chemical synthesis, and sustainable halide catalysis.

引用

页数：11

共 68 条

[1] Synthesis of 4,7-indoloquinones from indole-7-carbaldehydes by Dakin oxidation [J].

Alamgir, Mahiuddin ;

Mitchell, Peter S. R. ;

Bowyer, Paul K. ;

Kumar, Naresh ;

Black, David StC. .

TETRAHEDRON, 2008, 64 (30-31) :7136-7142

[2] Nonstabilized Azomethine Ylides in the Mannich Reaction: Synthesis of 3,3-Disubstituted Pyrrolidines, Including Oxindole Alkaloids [J].

Buev, Evgeny M. ;

Moshkin, Vladimir S. ;

Sosnovskikh, Vyacheslav Y. .

JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (23) :12827-12833

[3]

Bugg TDH, 1998, NAT PROD REP, V15, P513

[4] A GENERAL AND EXPEDIENT METHOD FOR THE SOLID-PHASE SYNTHESIS OF 1,4-BENZODIAZEPINE DERIVATIVES [J].

BUNIN, BA ;

ELLMAN, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10997-10998

[5] Discovery of XEN907, a spirooxindole blocker of NaV1.7 for the treatment of pain [J].

Chowdhury, Sultan ;

Chafeev, Mikhail ;

Liu, Shifeng ;

Sun, Jianyu ;

Raina, Vandna ;

Chui, Ray ;

Young, Wendy ;

Kwan, Rainbow ;

Fu, Jianmin ;

Cadieux, Jay A. .

BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 2011, 21 (12) :3676-3681

[6] Antiproliferative Lactams and Spiroenone from Adlay Bran in Human Breast Cancer Cell Lines [J].

Chung, Cheng-Pei ;

Hsu, Chih-Ying ;

Lin, Jing-Hui ;

Kuo, Yueh-Hsiung ;

Chiang, Wenchang ;

Lin, Yun-Lian .

JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 2011, 59 (04) :1185-1194

[7] Recent advances in organocatalytic methods for the synthesis of disubstituted 2-and 3-indolinones [J].

Dalpozzo, Renato ;

Bartoli, Giuseppe ;

Bencivenni, Giorgio .

CHEMICAL SOCIETY REVIEWS, 2012, 41 (21) :7247-7290

[8] Pd-Catalyzed Assembly of Spirooxindole Natural Products: A Short Synthesis of Horsfiline [J].

Deppermann, Nina ;

Thomanek, Heike ;

Prenzel, Alexander H. G. P. ;

Maison, Wolfgang .

JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (17) :5994-6000

[9] CONVERSION OF TETRAHYDRO-BETA-CARBOLINE ALKALOIDS INTO OXINDOLES - STRUCTURE AND PARTIAL SYNTHESES OF MITRAPHYLLINE AND RHYNCOPHYLLINE [J].

FINCH, N ;

TAYLOR, WI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (07) :1318-&

[10] OXIDATIVE TRANSFORMATIONS OF INDOLE ALKALOIDS .1. PREPARATION OF OXINDOLES FROM YOHIMBINE - STRUCTURES AND PARTIAL SYNTHESES OF MITRAPHYLLINE, RHYNCOPHYLLINE AND CORYNOXEINE [J].

FINCH, N ;

TAYLOR, WI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (20) :3871-+

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