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Synlett 2018; 29(02): 219-224
DOI: 10.1055/s-0036-1589112
letter
© Georg Thieme Verlag Stuttgart · New York

Elemental Sulfur-Mediated Decarboxylative Redox Cyclization ­Reaction: Copper-Catalyzed Synthesis of 2-Substituted Benzo­thiazoles

Xin Wang
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Xiaotong Li
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Renhe Hu
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Zhao Yang
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Ren Gu
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Sai Ding
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Pengyi Li
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
,
Shiqing Han*
a   College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211816, P. R. of China   eMail: hanshiqing@njtech.edu.cn
b   Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai 200032, P. R. of China
› InstitutsangabenWe thank the National High Technology Research and Development Program of China (863 Program 2014AA022100), Six Talent Peaks Project in Jiangsu Province (No. 2015-SWYY-016) and Graduate Student Innovation Project in Jiangsu Province (Grant No. SJCX17_0287) for supporting this research.
Weitere Informationen

Publikationsverlauf

Received: 30. Juli 2017

Accepted after revision: 03. September 2017

Publikationsdatum:
27. September 2017 (online)

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Abstract

A S8-mediated directed decarboxylative redox-cyclization strategy for the synthesis of 2-substituted benzothiazoles from o-iodoanilines, arylacetic acids, and elemental sulfur catalyzed by cheap copper metal has been developed. This reaction is operationally simple, ligand-free, compatible with a wide range of functional groups, and provides the desired products in good to excellent yields. In addition, a gram-scale experiment was carried out to furnish PMX 610, an antitumor drug.

Key words

benzothiazoles - decarboxylative cyclization - o-iodoanilines - arylacetic acids - elemental sulfur

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589112.
  • Supporting Information
 

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  • 16 General Procedure for the Synthesis of Benzothiazoles A mixture of o-iodoaniline (0.5 mmol, 1 equiv), arylacetic acid (0.6 mmol), elemental sulfur (1.5 mmol), Cu(OAc)2·H2O (20 mmol%), and NaOH (1.0 mmol) in DMSO (3 mL) was put into a sealed pressure vessel (25 mL) containing a magnetic stirring bar. The tube was purged with nitrogen three times, and then capped and stirred in a preheated oil bath at 130 °C for 24 h. The reaction mixture then cooled to r.t. and extracted with EtOAc (3 × 10 mL), the organic layer was washed with sat. NaCl (2 × 10 mL), dried over anhydrous Na2SO4, evaporated under vacumm, and then purified by silica gel column chromato­graphy (PE–EtOAc 200:1) to give pure compound 3aa in 98% yield. Selected Spectral Data for 2-Phenylbenzothiazole (3aa) 1H NMR (300 MHz, CDCl3): δ = 8.09–8.11 (m, 3 H), 7.90 (d, J = 7.8 Hz, 1 H), 7.48–7.52 (m, 4 H), 7.38 (t, J = 7.5 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 168.0, 154.1, 135.1, 133.6, 130.9, 129.0, 127.5, 126.2, 125.1, 123.2, 121.6.