New Insights in Frustrated Lewis Pair Chemistry with Azides

被引：20

作者：

Boom, Devin H. A. ^{[1
]}

Jupp, Andrew R. ^{[1
]}

Nieger, Martin ^{[2
]}

Ehlers, Andreas W. ^{[1
,3
]}

Slootweg, J. Chris ^{[1
]}

机构：

[1] Univ Amsterdam, Vant Hoff Inst Mol Sci, Sci Pk 904, NL-1090 GD Amsterdam, Netherlands

[2] Univ Helsinki, Dept Chem, AI Virtasen Aukio 1,POB 55, FIN-00014 Helsinki, Finland

[3] Univ Johannesburg, Sci Fac, Dept Chem, POB 254, Johannesburg, South Africa

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 58期

关键词：

azides; density functional calculations; frustrated Lewis pairs; heterocycles; isocyanates; C-H AMINATION; REPRESENTATIVE ORGANIC AZIDES; N-HETEROCYCLIC CARBENES; CYCLO-OLIGOMERIZATION; STAUDINGER REACTION; SI-H; COMPLEXES; ACTIVATION; HYDROGEN; IMIDAZOLIN-2-IMINATO;

D O I：

10.1002/chem.201902710

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The geminal frustrated Lewis pair (FLP) tBu(2)PCH(2)BPh(2) (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes-N-3 and tBu-N-3 are used. The reaction of 1 with Me3Si-N-3 is believed to follow the same course, yet subsequent N-2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

引用

页码：13299 / 13308

页数：10

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