Hydroboration without a B-H bond: reactions of the borinium cation [(iPr2N)2B]+ with alkyne, nitrile, ketone and diazomethane

被引：16
|
作者：
Major, Christopher J. [1 ]
Bamford, Karlee L. [1 ]
Qu, Zheng-Wang [2 ]
Stephan, Douglas W. [1 ]
机构：
[1] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada
[2] Univ Bonn, Mulliken Ctr Theoret Chem, Beringstr 4, D-53115 Bonn, Germany
来源：
CHEMICAL COMMUNICATIONS | 2019年 / 55卷 / 35期
基金：
加拿大自然科学与工程研究理事会;
关键词：
ZETA-VALENCE QUALITY; AUXILIARY BASIS-SETS; LEWIS-ACID; BORENIUM IONS; CHEMISTRY; BORON; HYDROGENATION; ELECTROPHILES; BORYLATION; ACTIVATION;
D O I：
10.1039/c9cc01302d
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The borinium cation [(iPr(2)N)(2)B](+) (1(+)) is shown to react with PhCCH, PhCN, Ph2CO, and Ph2CN2 to effect a net hydroboration, affording borenium complexes of the form [(iPr(2)N)B(iPrN?CMe2)(L)][B(C6F5)(4)] (L = CH?CHPh 2, N?CHPh 3, OCHPh(2)4, NHNCPh(2)5). The nature and reaction of 1(+) with PhCCH was probed computationally and the reduction of these unsaturates is shown to occur via hydride transfer from an isopropyl group to the alkyne, thus effecting hydroboration without a B-H bond.
引用
收藏
页码：5155 / 5158
页数：4
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