Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (12): 4815-4824.DOI: 10.6023/cjoc202106014 Previous Articles     Next Articles

ARTICLES

可见光催化的1,6-烯炔参与的Kharasch加成反应

耿芳洲a,b, 王世超a, 宋克贤a, 郝文娟a,b,*(), 姜波a,b,*()   

  1. a 江苏师范大学化学与材料科学学院 江苏徐州 221116
    b 江苏师范大学敬文书院 江苏徐州 221116
  • 收稿日期:2021-06-07 修回日期:2021-07-14 发布日期:2021-07-19
  • 通讯作者: 郝文娟, 姜波
  • 作者简介:
    † 共同第一作者
  • 基金资助:
    国家自然科学基金(21971090); 江苏省品牌专业基金和国家级大学生创新创业训练计划(202010320060Z)

Visible-Light-Driven Photocatalytic Kharasch-Type Addition of 1,6-Enynes

Fangzhou Genga,b, Shichao Wanga, Kexian Songa, Wenjuan Haoa,b(), Bo Jianga,b()   

  1. a School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
    b C.W. Chu College, Jiangsu Normal University, Xuzhou, Jiangsu 221116
  • Received:2021-06-07 Revised:2021-07-14 Published:2021-07-19
  • Contact: Wenjuan Hao, Bo Jiang
  • About author:
    † These authors contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China(21971090); Top-notch Academic Programs Project of Jiangsu Higher Education Institutions and National College Studentʼs Innovation and Entrepreneurship Training Program(202010320060Z)

A new visible-light-driven photocatalytic Kharasch-type addition of 1,6-enynes was reported. By using the characteristics of the in-situ-generation of trihalomethyl radicals from photocatalytic reduction of trichloromethane bromide and carbon tetrabromide, fac-Ir(ppy)3-catalyzed Kharasch-type addition of 1,6-enynes of these polyhalogenated hydrocarbon substrates at room temperature was conducted under visible-light irradiation, regioselectively affording 1-indanone derivatives with an exocyclic double bond and a quaternary carbon in moderate to good yields. Based on the experimental results and literature reports, a reasonable reaction mechanism was proposed, which involved the in-situ-generation of trihalomethyl radicals, radical-induced addition-cyclization and radical cross coupling. In addition, this protocol featured wide substrate scope, high functional group compatibility, 100% atomic utilization, and mild conditions as well as simple operation. It provides a green, mild, and efficient synthetic strategy for the construction of 1-indanone skeleton with potential application, which is consistent with the concept of green chemistry.

Key words: Kharasch-type addition, photocatalysis, 1,6-enynes, 1-indanones