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Synlett 2017; 28(03): 280-288
DOI: 10.1055/s-0036-1588128
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© Georg Thieme Verlag Stuttgart · New York

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

Brad P. Carrow*
Department of Chemistry, Princeton University, Princeton, NJ 08544, USA   Email: [email protected]
,
Liye Chen
Department of Chemistry, Princeton University, Princeton, NJ 08544, USA   Email: [email protected]
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Further Information

Publication History

Received: 02 November 2016

Accepted after revision: 01 December 2016

Publication Date:
10 January 2017 (online)

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Abstract

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-PAd3 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

Key words

phosphine - ligand - catalysis - cross-coupling - palladium - ­diamondoid
 

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