Lithium‐Aluminate‐Catalyzed Hydrophosphination Applications

Abstract

Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies,l ithium phosphidoaluminate iBu 3 AlPPh 2 Li(THF) 3 has been tested as ac atalyst for hydrophosphination of alkynes,a lkenes,a nd carbodiimides.B ased on the collective evidence of stoichiometric reactions,NMR monitoring studies,kinetic analysis,and DFT calculations,amechanism involving deprotonation, alkyne insertion, and protonolysis is proposed for the [iBu 3 AlHLi] 2 aluminate catalyzedh ydrophosphination of alkynes with diphenylphosphine.T his study enhances further the development of transition-metal-free,a tom-economical homogeneous catalysis using common sustainable main-group metals.

Photocatalytic Hydrophosphination with Air-Stable and Commercially Available Bis(acetylacetonato)copper(II) (Cu(acac)2)

“…Hydrophosphination of styrene was examined first due to its common use in recent studies. 41,42,43,44 A chloroform-d1 solution of styrene was treated with 2 equiv. of phenylphosphine in the presence of 5 mol % of 1.…”

An unusual mixed-valence cobalt dimer as a catalyst for the anti-Markovnikov hydrophosphination of alkynes

“…[34][35][36] Among the various 3d metal ion catalysts unveiled, only a limited number of catalysts are capable of adding P-H across alkynes for both terminal and internal alkynes. [37][38][39][40][41] However, the functional group at the propargylic position is seldom explored. This demands an alternative strategy for the catalyst design, and in particular, the employed ligand must anchor the metal ion with a less vacant site for coordination to avoid catalyst poisoning by the products arising from the reaction.…”

Fast and Chemoselective Addition of Highly Polarized Lithium Phosphides Generated in Deep Eutectic Solvents to Aldehydes and Epoxides

“…[17] Very recently, Mulvey et al [18] have extended this field to maingroup-mediated organic transformations by developing an efficient and smart methodology to create CÀ P bonds by metalation of HPPh 2 with mixed-metal lithium aluminates followed by reaction with a variety of alkynes. [18,19] However, these synthetic methodologies: i) usually require a large excess of catalyst/oxidant, ligand, or a PÀ H source (low atom and step economies); ii) need to be conducted under strictly anhydrous conditions; iii) involve expensive metal catalysts; and iv) are limited by a poor functional group tolerance. These shortcomings (among which is also included the notorious strong coordination of the phosphorus moiety to the metal catalyst) have precluded the wide application of these synthetic methodologies.…”