Cross‐Electrophile C−PIIICoupling of Chlorophosphines with Organic Halides: Photoinduced PIIIand Aminoalkyl Radical Generation Enabled by Pnictogen Bonding

Abstract

AbstractPnictogen bonding (PnB) has gained recognition as an appealing strategy for constructing novel architectures and unlocking new properties. Within the synthetic community, the development of a straightforward and much simpler protocol for cross‐electrophile C−PIIIcoupling remains an ongoing challenge with organic halides. In this study, we present a simple strategy for photoinduced PnB‐enabled cross‐electrophile C−PIIIcouplings using readily available chlorophosphines and organic halides via merging single electron transfer (SET) and halogen atom transfer (XAT) processes. In this photomediated transformation, the PnB formed between chlorophosphines and alkyl amines facilitates the photogeneration of PIIIradicals andα‐aminoalkyl radicals through SET. Subsequently, the resultingα‐aminoalkyl radicals activate C−X bonds via XAT, leading to the formation of carbon radicals. This methodology offers operational simplicity and compatibility with both aliphatic and aromatic chlorophosphines and organic halides.