Synlett 2018; 29(01): 116-120
DOI: 10.1055/s-0036-1588549
letter
© Georg Thieme Verlag Stuttgart · New York

Iodine-Catalyzed Regioselective Sulfenylation of 4H-Pyrido[1,2-a]pyrimidin-4-ones with Sulfonyl Hydrazides

Wenjie Liu
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
Guangdong Cosmetics Engineering & Technology Research Center, Guangzhou, 510006, P. R. of China   Email: wangshaohua108@163.com
,
Shaohua Wang*
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
Guangdong Cosmetics Engineering & Technology Research Center, Guangzhou, 510006, P. R. of China   Email: wangshaohua108@163.com
,
Zhihao Cai
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
,
Ziying Li
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
,
Jianwen Liu
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
,
Anda Wang
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Guangzhou 510006, P. R. of China
› Author Affiliations
The work was financially supported by the Project for Enhanced Innovation of Guangdong Pharmaceutical University, Provincial Experimental Teaching Demonstration Center of Chemistry and Chemical Engineering.
Further Information

Publication History

Received: 16 June 2017

Accepted after revision: 18 July 2017

Publication Date:
22 August 2017 (eFirst)

Abstract

A simple and efficient method for direct sulfenylation of 4H-pyrido[1,2-a]pyrimidin-4-ones with sulfonyl hydrazides has been developed. The transformation is catalyzed by iodine under metal-free conditions with high regioselectivity and good functional-group tolerance.

Supporting Information

 
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  • 18 3-(Phenylsulfanyl)-4H-pyrido[1,2-a]pyrimidin-4-one (3a); Typical Procedure
    1a
    (29 mg, 0.2 mmol), PhSO2NHNH2 (2a; 41 mg, 0.24 mmol), I2 (10mg, 20 mol%), and EtOH (0.5 mL) were stirred in a sealed tube at 100 °C for 12 h. When the reaction was complete (TLC), EtOAc (10 mL) was added. The organic phase was washed with brine (2 × 3 mL) and dried (Na2SO4). The solvent was removed, and the crude product was separated by column chromatography [silica gel, PE–EtOAc (3:1)] to give a white solid; yield: 40 mg (78%); mp 106–108 °C. 1H NMR (400 MHz, CDCl3): δ = 9.09 (d, J = 7.2 Hz, 1 H), 8.46 (s, 1 H), 7.80–7.76 (m, 1 H), 7.69 (m, 1 H), 7.39 (m, 2 H), 7.30–7.27 (m, 2 H), 7.24–7.19 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 157.5, 156.7, 151.3, 136.4, 134.5, 130.1, 129.2, 127.7, 127.1, 126.7, 116.4, 111.6. ESI-MS: m/z = 255 [M + H]+. HRMS (ESI): m/z [M + H]+ calcd for C14H11N2OS: 255.0593; found: 255.0597. Anal. Calcd C, 66.12; H, 3.96; N, 11.02. Found: C, 66.03; H, 3.91; N, 10.90.