高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (1): 118-124.doi: 10.7503/cjcu20190424

• 有机化学 • 上一篇    下一篇

无金属条件下I2/TBHP体系促进磺酰肼与烯醇硅醚自由基偶联反应合成α-磺酰基酮

唐裕才(),屈煌,张文熙,王菲菲,王钢   

  1. 洞庭湖生态经济区建设与发展湖南省协同创新中心, 湖南文理学院化学与材料工程学院, 常德 415000
  • 收稿日期:2019-07-26 出版日期:2019-12-02 发布日期:2019-12-02
  • 通讯作者: 唐裕才 E-mail:yctang1009@163.com
  • 基金资助:
    国家自然科学基金批准号:(51703062);湖南文理学院博士科研启动基金批准号:(17BSQD32);湖南文理学院校级科研项目资助批准号:(E06018073)

Synthesis of α-Sulfonyl Ketones via I2/TBHP Promoted Radical Sulfonylation of Silyl Enol Ethers with Sulfohydrazides under Mild Conditions

TANG Yucai(),QU Huang,ZHANG Wenxi,WANG Feifei,WANG Gang   

  1. Hunan Province Cooperative Innovation Center for the Construction & Development of Dongting Lake Ecologic Economic Zone, College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde 415000, China
  • Received:2019-07-26 Online:2019-12-02 Published:2019-12-02
  • Contact: Yucai TANG E-mail:yctang1009@163.com
  • Supported by:
    ? Supported by the National Natural Science Foundation of China No(51703062);the Start-up Foundation for Doctors of Hunan University of Arts and Science, China No(17BSQD32);and the Scie.pngic Research Fund of Hunan University of Arts and Science, China No(E06018073)

摘要:

在以单质碘(I2)为催化剂, 叔丁基过氧化氢(TBHP)为氧化剂条件下, 使烯醇硅醚与各种取代的磺酰肼发生自由基磺酰化反应, 经自由基加成和氧化反应, 再水解脱去三甲基碘硅烷(Me3SiI), 在最优条件下, 以22%~72%的收率合成了22种具有不同取代基的α-磺酰基酮衍生物, 采用核磁共振波谱表征了终产物的结构. 实验结果表明, 该方法具有良好的底物普适性, 氟、 氯、 硝基、 三氟甲基、 呋喃和萘等取代基团均能顺利发生转化, 得到相应的目标产物.

关键词: α-磺酰基酮;, 烯醇硅醚, 磺酰肼, 自由基反应

Abstract:

A I2/TBHP mediated reaction of readily prepared silyl enol ethers with sulfonylhydrazides was developed for the synthesis of α-sulfonyl ketones under mild conditions. Twenty-two α-sulfonyl ketone derivatives were obtained in 22%—72% yields under the optimized reaction conditions. Their structures were confirmed by nuclear magnetic resonance spectroscopy(NMR). Moreover, the present catalytic protocol exhibited good functional group tolerance and substrate applicability, and various substituents such as halogen, nitro, trifluoromethyl, furan and naphthalene can be successfully converted to corresponding α-sulfonyl ketones. The preliminary mechanistic studies disclose that the reaction may proceed via a radical pathway.

Key words: α-Sulfonyl ketone;, Silyl enol ether, Sulfonylhydrazide, Radical reaction

中图分类号: