New Approaches toward Building C_sp−P bond: A Two‐Decade Overview

Abstract

Since the review of Savignac, the past 20 years have seen significant progresses on the synthesis of alkynylphosphorus compounds considerably expanding the original and rather limited organic toolbox. This comprehensive review explores the latest and potentially greener methodologies using sustainable catalysis or direct metal‐free couplings from stable and easy to handle precursors. Recent progress and mechanistic insights for metal‐catalyzed reactions with a particular emphasis on copper, palladium, nickel and silver catalytic systems, photocatalytic and metal‐free reactions are detailed covering most of the publications related to this field since 2000 until March 2022.

Unveiling the Three-Component Phosphonylation on Alkynylaldehydes: Toolbox toward Fluorescent Molecules

“…Phosphorus is a vital element that has never failed to fascinate with its distinguished properties, and in an immense number of special molecules, phosphorus plays a key role; therefore, the development of prevalent strategies for phosphonation is always undiminished. Over the past decades, the C–P bond formation using transition-metal-catalyzed reactions on alkenes and alkynes with phosphonate esters has been much exploited …”

Transition‐Metal‐Free Synthesis of Alkynylphosphine Oxides from Terminal Alkynes and Chlorodiphenylphosphine Oxide

“…[5] As a result, the synthetic approaches to alkynylphosphine oxides have been intensively studied in the past two decades. [6] Among them, much efforts have been devoted to the alkynylation of secondary phosphine oxides. For example, several research groups disclosed the dehydrogenative cross-couplings of terminal alkynes with secondary phosphine oxides to build such frameworks under different homo-and heterogenous conditions (Scheme 1a).…”

“…Besides, the alkynylphosphine oxide skeleton can be found in some bioactive molecules [5] . As a result, the synthetic approaches to alkynylphosphine oxides have been intensively studied in the past two decades [6] . Among them, much efforts have been devoted to the alkynylation of secondary phosphine oxides.…”