Tri(1-adamantyl) phosphine: Exceptional Catalytic Effects Enabled by the Synergy of Chemical Stability, Donicity, and Polarizability

被引：23

作者：

Carrow, Brad P. ^{[1
]}

Chen, Liye ^{[1
]}

机构：

[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

来源：

SYNLETT | 2017年 / 28卷 / 03期

关键词：

phosphine; ligand; catalysis; cross-coupling; palladium; diamondoid; TRANSITION-METAL-COMPLEXES; MIYAURA COUPLING REACTIONS; CARBON-CARBON BONDS; C-O BOND; ROOM-TEMPERATURE; ARYL CHLORIDES; REDUCTIVE ELIMINATION; PALLADIUM CATALYSTS; ARYLBORONIC ACIDS; CRYSTAL-STRUCTURE;

D O I：

10.1055/s-0036-1588128

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Tri(1-adamantyl) phosphine, a simple yet long-absent homoleptic phosphine, has finally been prepared. The simplicity of this compound beguiles its exceptional properties. The electron-releasing character eclipses all other alkylphosphines. The phosphine geometry and overall size are also more compact than anticipated, which may occur as a result of dispersion forces. We believe the donicity, marked resistance towards cyclometallation or P-C bond scission, and also substantial polarizability engendered by the three diamondoid fragments together account for the phenomenal performance of Pd-PAd(3) catalysts during Suzuki-Miyaura coupling reactions. A correlation analysis is also described that provides support for polarizability as a potentially general influence on the properties of tertiary phosphines. 1 Introduction 2 Synthesis of Tri(1-adamantyl) phosphine 3 Reactions of Tri(1-adamantyl) phosphine Palladium Complexes 4 Electronic and Steric Properties of Tri(1-adamantyl) phosphine 5 Conclusion

引用

页码：280 / 288

页数：9

共 89 条

[71] PREPARATION AND STRUCTURE OF HEXAKIS[(TRIALKYLPHOSPHANE)AURIO(I)]METHANIUM(2+) SALTS [(LAU)6C]2+(X-)2 WITH L = ET3P, IPR3P AND X = BF4-, B3O3F4- [J].