催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (3): 472-476.DOI: 10.3724/SP.J.1088.2011.01018

• 研究论文 • 上一篇    下一篇

Cu(OTf)2 催化苄基卤代物与三丁基烯丙基锡的偶联反应

于晓强 1, 马永洁 1, 赵自然 2, 许占威 1, 包明 1   

  1. 1 大连理工大学精细化工国家重点实验室, 辽宁大连 116012; 2 吉林大学第一医院整形外科, 吉林长春 130021
  • 收稿日期:2010-10-15 修回日期:2010-12-08 出版日期:2011-03-04 发布日期:2014-08-01

Cross-Coupling Reaction of Benzylic Halides with Allyltributylstannane Catalyzed by Cu(OTf)2

YU Xiaoqiang1, MA Yongjie1, ZHAO Ziran2,*, XU Zhanwei1, BAO Ming1,*   

  1. 1State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, Liaoning, China; 2Department of Plastic and Reconstructive Surgery, The First Hospital of Jilin University, Changchun 130021, Jilin, China
  • Received:2010-10-15 Revised:2010-12-08 Online:2011-03-04 Published:2014-08-01

PDF

1136

摘要： 研究了苄基卤代物与三丁基烯丙基锡的偶联反应, 当以 10 mol%Cu(OTf)2 为催化剂, CH2Cl2 为溶剂时, 1-氯甲基-4-苯基萘与三丁基烯丙基锡于室温反应 1 h, 交叉偶联反应产物 1-(3-丁烯基)-4-苯基萘 (3b) 收率即达 93%. 结果表明, 芳环含供电子基的底物反应活性较高, 在室温反应几分钟即可完成, 而芳环含吸电子基的底物反应活性低. 反应产物 3b, 1-溴-4-(3-丁烯基) 萘 (3c) 和 1-(3-丁烯基)-4-硝基萘 (3f) 未见报道, 且其结构经表征确认.

关键词: 苄基卤代物, 三丁基烯丙基锡, 三氟甲基磺酸铜, 偶联反应

Abstract: Cross-coupling reaction of benzylic halides with allyltributylstannane was investigated. Desired cross-coupling products were obtained in satisfactory yields using Cu(OTf)2 as the catalyst. For example, cross-coupling product 1-(but-3-en-1-yl)-4-phenylnaphthalene (3b) was obtained in 93% yield when the reaction of 1-chloromethyl-4-phenylnaphthalene with allyltributylstannane was carried out in the presence of 10 mol% of Cu(OTf)2 in CH2Cl2 at room temperature for 1 h. The reaction of a substrate bearing an electron-donating group on the aromatic ring was completed in a few minutes, whereas the reaction of a substrate having an electron-withdrawing group on the aromatic ring needed prolonged reaction time. 3b, 1-bromo-4-(but-3-en-1-yl)naphthalene (3c), and 1-(but-3-en-1-yl)-4-nitronaphthalene (3f) were unknown compounds and their structure was confirmed by 1H NMR, 13C NMR, IR, and HRMS.

Key words: benzylic halide, allyltributylstannane, copper(II) trifluoromethanesulfonate, coupling reaction