Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (2): 766-775.DOI: 10.6023/cjoc202007018 Previous Articles     Next Articles



席鑫1, 张公平1, 李建成1, 黄艳婷1, 蒋文军1, 吴鹏1, 朱红平1,*()   

  1. 1 厦门大学化学化工学院 固体表面物理化学国家重点实验室 厦门 361005
  • 收稿日期:2020-07-06 修回日期:2020-08-17 发布日期:2020-09-16
  • 通讯作者: 朱红平
  • 作者简介:
    * Corresponding author. E-mail:
  • 基金资助:
    国家自然科学基金面上(21972112); 国家自然科学基金面上(21673191)

Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C6F5)3

Xin Xi1, Gongping Zhang1, Jiancheng Li1, Yanting Huang1, Wenjun Jiang1, Peng Wu1, Hongping Zhu1,*()   

  1. 1 State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2020-07-06 Revised:2020-08-17 Published:2020-09-16
  • Contact: Hongping Zhu
  • Supported by:
    the General Project of National Natural Science Foundation of China(21972112); the General Project of National Natural Science Foundation of China(21673191)

Five alkyne compounds of varied novel substituents as Mes2HSiC≡CPh (1, Mes=2,4,6-Me3C6H2), [tBuC- (NAr)2]GeC≡CPh (2, Ar=2,6-iPr2C6H3), [PhC(NtBu)2]SnC≡CPPh2 (3), [HC(CMe)2(NAr)2]SnC≡CPPh2, (4) and [HC(C- Me)2(NAr)2]ZnC≡CPPh2 (5) have been synthesized. Compounds 1 and 2 reacted with B(C6F5)3 by the 1,1-carboboration to give compounds (Ph)(Mes2HSi)C=C(C6F5)B(C6F5)2 (6) and {[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7), respectively, where (F5C6)3B/Mes2HSi group exchange was suggested to occur initially for the former reaction while the (F5C6)3B/ [tBuC(NAr)2]Ge exchange was for the latter one. Compound 6 is a acyclic alkene whereas 7 is viewed as a germanaboracyclo- butene owing to a strong GeII→B donor-acceptor bonding being a GeII/B frustrated Lewis pair (FLP). Compounds 3~5 reacted with B(C6F5)3 to undergo a ligand coordinated metal group/B(C6F5)3 exchange followed by bonding of metal group at PPh2, resulting in the formation of a novel type of intramolecular zwitterionic alkynes [PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3(8), [HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3 (9), and [HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10), respectively. Compounds 1~10 have been characterized by spectroscopy and elemental analysis, of which 4, 6, 7, and 10 are further authenticated by X-ray crystallography. The mechanisms of these reactions are discussed.

Key words: alkynes of novel substituents, B(C6F5)3, 1,1-carboboration, group exchange reaction, alkenes of novel substituents