Reactivity of frustrated Lewis pairs with BOC protected diazocarboxylates: FLP capture of diazene

被引：8

作者：

Hussain, Zahid ^{[1
]}

Luo, Yong-An ^{[1
]}

Wu, Yile ^{[1
]}

Qu, Zheng-Wang ^{[2
]}

Grimme, Stefan ^{[2
]}

Stephan, Douglas W. ^{[1
,3
]}

机构：

[1] Ningbo Univ, Inst Drug Discovery Technol, Ningbo 315211, Zhejiang, Peoples R China

[2] Rhein Friedrich Wilhelms Univ Bonn, Clausius Inst Phys & Theoret Chem, Mulliken Ctr Theoret Chem, Beringstr 4, D-53115 Bonn, Germany

[3] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada

来源：

CHEMICAL COMMUNICATIONS | 2023年 / 59卷 / 41期

关键词：

BASIS-SETS; N-2; REDUCTION; CHEMISTRY; ACCURATE; DESIGN;

D O I：

10.1039/d3cc01571h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reactions of (tBuO(2)CN)(2) with FLPs are examined. B(C6F5)(3) interacts with the carbonyl oxygen atoms inducing loss of CH2=CMe2; however, in the presence of basic donors, the protons are intercepted affording the salts [Hbase](2) [((C6F5)(3)BO2CN)(2)] (base = tBu(3)P 1, NC(5)H(2)Ph(3)2, HNC(5)H(6)Me(4)3). In contrast, in the presence of (o-Tol)(3)P, a proton transfers to the diazo-N atom affording (o-Tol)(3)PN(CO(2)tBu)NHB(C6F5)(3)4. Further addition of B(C6F5)(3) to 4 prompts loss of olefin CH2=CMe2 and CO2 affording (o-Tol)(3)PNHNHB(C6F5)(3)5. The course of these reactions is examined by extensive DFT calculations. The nature of 5 is consistent with the FLP reduction of a diazene fragment.

引用

页码：6191 / 6194

页数：4

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