Palladium-Catalyzed C-P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide.

Holly Mcerlain,Leanne M Riley,Andrew Sutherland

doi:10.1021/acs.joc.1c02172

Abstract

An iodide-accelerated, palladium-catalyzed C–P bond-forming reaction of aryl nonaflates is described. The protocol was optimized for the synthesis of aryl phosphine oxides and was found to be tolerant of a wide range of aryl nonaflates. The general nature of this transformation was established with coupling to other P(O)H compounds for the synthesis of aryl phosphonates and an aryl phosphinate. The straightforward synthesis of stable, isolable aryl nonaflates, in combination with the rapid C–P bond-forming reaction allows facile preparation of aryl phosphorus target compounds from readily available phenol starting materials. The synthetic utility of this general strategy was demonstrated with the efficient preparation of an organic light-emitting diode (OLED) material and a phosphonophenylalanine mimic.

Highlights

Aryl phosphorus compounds are important due to their widespread application in organic, medicinal, and materials chemistry.1,2 As a consequence, carbon−phosphorus bond formation is a highly active area of research in organophosphorus chemistry
Aryl C−P bonds were formed via the reaction of Grignard or organolithium reagents with electrophilic phosphorus compounds
Aryl triflates have been explored as substrates,5,6e,7 but the high cost and reactive nature of reagents limits applications. This has led to the development of metal-catalyzed aryl C−P bond-forming reactions using mesylates and tosylates

Summary

Introduction

Aryl phosphorus compounds are important due to their widespread application in organic, medicinal, and materials chemistry. As a consequence, carbon−phosphorus bond formation is a highly active area of research in organophosphorus chemistry. Aryl C−P bonds were formed via the reaction of Grignard or organolithium reagents with electrophilic phosphorus compounds.. Despite the availability of aryl halides as coupling reagents, many complex arenes, natural product-based (e.g., steroids and amino acids), exist only in phenolic form. For this reason, Hirao-type reactions using activated sulfonates have been reported. Aryl triflates have been explored as substrates,5,6e,7 but the high cost and reactive nature of reagents limits applications. This has led to the development of metal-catalyzed aryl C−P bond-forming reactions using mesylates and tosylates.. This has led to the development of metal-catalyzed aryl C−P bond-forming reactions using mesylates and tosylates. For example, the Kwong group has demonstrated the effective phosphorylation of aryl mesylates and tosylates using low catalyst loadings of

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Conclusion