Hydrophosphorylation of aliphatic alkynes catalyzed by CuNPs/ZnO for the synthesis of vinyl phosphonates. A DFT study on the reaction mechanism

Abstract

A DFT study on the reaction mechanism for the synthesis of vinyl phosphonates catalyzed by CuNPs/ZnO. Essential role of the solvent and the catalyst support.

Phosphorylation of Alkenyl and Aryl C–O Bonds via Photoredox/Nickel Dual Catalysis

“…Traditionally, phosphorylation of organometallic reagents with electrophilic phosphorus reagents is widely used . Since the 1980s, transition metal-catalyzed cross-couplings of organohalides and carboxylic acids with P­(O)–H compounds as well as addition of P­(O)-H compounds to alkynes have emerged as efficient methods to generate C­(sp 2 )–P bonds . However, there are still some drawbacks such as high catalyst loading, harsh reaction conditions, and limited substrate scope as well as the use of toxic and expensive organohalides.…”

Hydrothiolation of alkynes with thiol–catechol derivatives catalysed by CuNPs/TiO2: exploring the reaction mechanism by DFT calculations

“…Although the exact mechanism involved for this reaction was difficult to ascertain, based on our previously reported results 25 and those by other groups in the same area, and with the aid of some additional experiments, the formation of copper acetylides as reaction intermediates (deuterated-vinyl sulphide product was obtained when starting from 3-deuteriopropiolamide) and the participation of radical species (hydrothiolation was also efficient in the presence of TEMPO) could be disregarded.…”

“…Since the reaction could be considered to start with the CuNPs/TiO 2 nanocatalyst activating the alkyne and/or the thiol, it was necessary to establish the way in which the support surface could be attached to copper so as to stabilize the metal nanoparticles. Taking into account our previous results on computational calculations for a similar copper nanocatalyst, 25 and assuming that copper would be attached to the support through both TiO 2 oxygen atoms, we modelled different plausible structures for our CuNPs/TiO 2 nanocatalyst. As can be seen from Fig.…”

“…In order to contribute to the rational design of more selective and active catalysts, it is crucial to have an in-depth understanding of the mechanistic aspects involved in each catalytic process. To this end, and inspired by our permanent interest in the use of computational methods for unveiling the main mechanistic aspects of organic transformations, 24 specially those promoted by supported metal nanocatalysts, 25 we present herein a computational theoretical study, based on DFT methods, to shed light on the high stereoselectivity observed in the hydrothiolation of activated alkynes with thiols bearing a catechol group catalysed by CuNPs/TiO 2 .…”

Preparation of Vinylphosphonates from Ketones Promoted by Tf2O

“…In 2001, the first rhodium catalyzed P­(O)–H compounds reacted with alkynes was developed by Zhao and co-workers . Since then, a series of metal-catalyzed reactions between alkynes and phosphorus compounds have been vigorously covered. , Besides precious metal, copper, molybdenum, and manganese were also developed to catalyze the reaction.…”