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Synlett 2022; 33(01): 16-26
DOI: 10.1055/s-0037-1610782
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α-Cationic Phosphines: from Curiosities to Powerful Ancillary Ligands

Christian J. Rugen
,
Manuel Alcarazo  ∗
This research has been funded by the Deutsche Forschungsgemeinschaft (Grant Numbers Al 1348/4-2, Al 1348/4-3, Al 1348/8-1, Al 1348/9-1, INST 186/1324-1, INST 186/1237-1, and INST 186/1298-1).
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Abstract

The distinguishing feature of α-cationic phosphines is the presence of at least one substituent, normally (hetero)cyclic and positively charged, which is directly attached to the phosphorus atom. As result from this unique substitution pattern, the thus designed ligands depict significantly diminished donor properties if compared with their neutral counterparts. Thus, if in a hypothetical catalytic cycle, the step that determines the rate is facilitated by an increase of the electrophilicity at the metal center; then, the use of α-cationic ancillary phosphines can be highly beneficial. This fact, combined with their easy syntheses and stability, which allows an easy handling, make α-cationic phosphines a useful tool for the synthetic practitioner. Our research on the topic demonstrates that generally a remarkable ligand acceleration effect is observed when α-cationic phosphines are employed in Au(I)- and Pt(II)-promoted cycloisomerizations; moreover, in some cases even otherwise not operative transformations can be promoted. This Account describes how we entered into the topic, our efforts, and those of others to understand the coordination behavior of α-cationic phosphines and further develop their range of applications in catalysis; but it also identifies the drawbacks associated with their use, which limit their range of application.

1 Introduction

2 Polycationic Phosphines: Stronger Acceptors than Phosphites

3 Inconveniences Derived from the Use of (Poly)cationic phosphines

4 A Second Generation of Cationic Ligands: α-Pyridiniophosphines

5 Chiral α-Cationic Phosphines

6 α-Radical Phosphines and (Poly)cationic Phosphine Oxides

7 Conclusions and Outlook

Key words

α-cationic phosphines - ligand design - π-acid catalysis - ­hydroarylation - asymmetric catalysis - helicenes


Publication History

Received: 26 May 2021

Accepted after revision: 07 July 2021

Article published online:
09 August 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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