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Synlett 2019; 30(07): 851-856
DOI: 10.1055/s-0037-1611754
letter
© Georg Thieme Verlag Stuttgart · New York

Direct N-sec-Alkylation of Amides by Reaction of α-Halohydroxamates and Sulfonylindoles: An Approach to 3-Indolyl Methanamines

Yuan Chen
a   College of Pharmacy and Biological Engineering, Chengdu University, Chengdu City 610106, P. R. of China
b   College of Chemistry and Chemical Engineering, China West Normal University, Nanchong City 637002, P. R. of China   Email: kangtairan@sina.com
,
Xiaoqiang Guo
a   College of Pharmacy and Biological Engineering, Chengdu University, Chengdu City 610106, P. R. of China
,
Chuang Zhou
a   College of Pharmacy and Biological Engineering, Chengdu University, Chengdu City 610106, P. R. of China
,
Lianmei Chen
a   College of Pharmacy and Biological Engineering, Chengdu University, Chengdu City 610106, P. R. of China
,
Tairan Kang  *
a   College of Pharmacy and Biological Engineering, Chengdu University, Chengdu City 610106, P. R. of China
b   College of Chemistry and Chemical Engineering, China West Normal University, Nanchong City 637002, P. R. of China   Email: kangtairan@sina.com
› Author AffiliationsWe are grateful for financial support from the National Natural Science Foundation of China (NO. 21672172), the project of Youth Science and Technology Innovation Team of Sichuan Province, China (2017TD0008); the Education Department of Sichuan Province (NO. 15CZ0016).
Further Information

Publication History

Received: 29 November 2018

Accepted after revision: 20 February 2019

Publication Date:
28 March 2019 (online)

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Abstract

A catalyst-free, base-mediated N-sec-alkylation of amides by reaction of sulfonylindoles and α-halohydroxamates has been developed. The N-sec-alkylation of amides reaction is based on an intermolecular nucleophilic addition of vinylogous imine with N-(benzyl­oxy)meth-acrylamide/azaoxyallyl cations formed in situ and represents a simple way to give polyfunctionalized 3-indolyl methanamines in good to excellent yields.

Key words

3-indolyl methanamines - azaoxyallyl cations - vinylogous imine - sulfonylindoles - α-halohydroxamates

Supporting Information

 

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  • 14 Typical procedure and characterization data for 3a: To a solution of sulfonylindole 1a (0.1 mmol) in 1,4-dioxane (1.0 mL) was added α-halohydroxamates 2a (0.15 mmol) and Na2CO3 (0.3 mmol). The reaction mixture was stirred at 80 °C until the starting material sulfonylindole was consumed (monitored by TLC). After cooling to room temperature, the solvent was removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel [flash column chromatography eluent, petroleum ether/ethyl acetate (6:1–4:1, v/v)] to give the pure product 3a (37 mg, 91% yield) as an oil. 1H NMR (400 MHz, CDCl3): δ = 7.37–7.34 (m, 3 H), 7.30–7.27 (m, 3 H), 7.23–7.21 (m, 1 H), 7.16–7.13 (m, 3 H), 7.11–7.08 (m, 1 H), 6.96–6.92 (m, 1 H), 6.77 (d, J = 6.94 Hz, 2 H), 5.48 (s, 1 H), 5.35 (s, 1 H), 4.95 (s, 1 H), 4.59 (d, J = 8.68 Hz, 1 H), 3.96 (d, J = 8.70 Hz, 1 H), 2.20 (s, 3 H), 2.06 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 171. 4, 141.1, 139.9, 135.1, 134.9, 134.4, 129.5, 129.3, 128.6, 128.5, 128.4, 128.3, 128.1, 127.0, 126.8, 121.3, 119.8, 119.7, 117.3, 110.3, 108.7, 78.6, 57.4, 20.4, 12.5. HRMS: m/z [M+H]+ calcd for C27H26N2O2: 410.2013; found: 410.2016.
  • 15 CCDC 1546337 (3g) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data request/cif.