Chinese Journal of Organic Chemistry >
Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C6F5)3
Received date: 2020-07-06
Revised date: 2020-08-17
Online published: 2020-09-16
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.
Xin Xi , Gongping Zhang , Jiancheng Li , Yanting Huang , Wenjun Jiang , Peng Wu , Hongping Zhu . Synthesis of Alkynes Composed of the Novel Substituents and Their Reactions with B(C6F5)3[J]. Chinese Journal of Organic Chemistry, 2021 , 41(2) : 766 -775 . DOI: 10.6023/cjoc202007018
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