Palladium-catalyzed asymmetric hydrophosphorylation of alkynes: facile access to P-stereogenic phosphinates

Abstract

<p>A catalytic enantioselective synthesis of <italic>P</italic>-stereogenic alkenylphosphinates is developed through asymmetric hydrophosphorylation. This process is demonstrated on racemic phosphinates and leads to diverse <italic>P</italic>-stereogenic alkenylphosphinates directly.</p>

Nickel-Catalyzed Asymmetric Synthesis of P-Stereogenic Vinyl Phosphines

“…The acid additive might form a stable complex with the substrates with two hydrogen bonds, weakening the acid's effect. 2-Ethynylnaphtalene, 2-ethynylthiophene, and ethynylferrocene all reacted effectively in high yields, enantio-and regioselectivities (45)(46)(47). In addition, cyclopropylacetylene also reacted successfully in 67% yield with 51% ee and >20:1 rr (48) with no ring-opened product detected, excluding the radical mechanism.…”

“…Based on the experiments above, the mechanism is proposed in Scheme 5. 47,48 The Ni(0) complex I was converted into Ni(II) intermediate II in the presence of (PhO) 2 PO 2 H, followed by ligand exchange with secondary phosphine. Subsequent hydronickelation of the alkyne followed by reductive elimination to afford the final product IV.…”

Nickel/Brønsted acid dual-catalyzed regio- and enantioselective hydrophosphinylation of 1,3-dienes: access to chiral allylic phosphine oxides

“… 8 Recently, the enantioselective hydrofunctionalization of conjugated 1,3-dienes, allenes and alkynes with C-, 9 N-, 10 or S-nucleophiles 11 has attracted broad attention and has been developed as a powerful tool to synthesize chiral allylic compounds. 12 Asymmetric hydrophosphination (including hydrophosphonylation and hydrophosphinylation) 13 of 1,3-dienes with P–H nucleophiles is undoubtedly a straightforward and atom-efficient approach to construct chiral allylic organophosphorus compounds. A seminal study of enantioselective coupling of terminal 1,3-dienes and phosphine oxides affording a series of chiral α-methyl allylic phosphine oxides by palladium catalysis was demonstrated by Dong and coworkers in 2018 ( Fig.…”

Asymmetric Access of γ-Amino Acids and γ-Amino Phosphonic Acid Derivatives via Copper-Catalyzed Enantioselective and Regioselective Hydroamination

“…66 For phosphine substrates, the only example was Cu-catalyzed regioselective hydroamination of vinylphosphines reported by Miura, providing a new approach to α-aminophosphines though the asymmetric version was still preliminary. 67 Inspired by previous elegant works [65][66][67] and our continuous interest in constructing chiral organophosphorus compounds [68][69] and amino esters [70][71] , we herein presented a general method to attain γsubstituted-γ-amino esters and γ-substituted-γ-amino phosphonic acid derivatives by diastereo-and enantioselective Cu-catalyzed electrophilic amination of cinnamyl derivatives.…”