Recent Developments in the Addition of Phosphinylidene‐Containing Compounds to Unactivated Unsaturated Hydrocarbons: Phosphorus–Carbon Bond Formation by Hydrophosphinylation and Related Processes

Abstract

Summary The reactions of phosphinylidene-containing compounds with unactivated unsaturated hydrocarbons are reviewed. The review is organized by phosphorus-containing functional group types. Free-radical and metal-catalyzed additions of R1R2P(O)H to alkenes, alkynes, and related compounds, deliver functionalized organophosphorus compounds RP(O)R1R2, including H-phosphinates, phosphinates, tertiary phosphine oxides, and phosphonates. The review covers the literature up to February 2008.

Synthesis of dipeptide mimics based on amino phosphinate backbones and cyclic derivatives

“…Intramolecular cyclization gave cyclic phosphinate 23 as a mixture of four stereoisomers. Finally, hydrolysis with aqueous HCl to 24 was performed to decrease the number of possible stereoisomers and a 2:1-mixture of two diastereoisomers was observed in the 13 C-NMR-spectra. Alternatively, the alkylation of H-phosphinate 14 with α-methylene-γ-butyrolactone (25) gave also dipeptide mimic 24, but with no diastereoselectivity at all.…”

“…[11][12][13][14][15][16] An additional drawback for many applications is the high polarity of the phosphinate group. Herein we describe the synthesis of stereoisomerically pure GPI (1), a phosphinate with high binding affinity to the cancer specific zinc peptidase PSMA (prostate specific membrane antigen).…”

Recent Progress in Transition Metal-Catalyzed Addition Reactions of H–P(O) Compounds with Unsaturated Carbon Linkages

“…The yield is low (<30%). Treatment of Fe(CO) 5 or W(CO) 6 with HP(O)(OEt) 2 appears to generate M-P(O)(OEt) 2 species (M¼Fe, W), on the basis of 31 P NMR spectroscopy, which displays, for M¼W, a satellite band possibly arising from coupling 2 triggers a vigorously exothermic reaction affording diethyl cyclohexylphosphonate in 80% yield. However, the structure of these complexes has not been characterized further and mechanistic details remain to be clarified.…”

“…Similar addition reaction of H-phosphonates to cyclohexene proceeds when a mixture of cyclohexene (4 equiv. ), HP(O)(OR) 2 (R¼Me, Et, i Pr), metal carbonyl (10 mol%; Fe(CO) 5 , W(CO) 6 , Mo(CO) 6 or Cr(CO) 6 ), and a catalytic quantity of triethylamine is refluxed for 5 h under argon (Scheme 59) [62]. The yield is low (<30%).…”

Recent Advances in Metal-Catalyzed C–P Bond Formation

“…In hydrophosphination, a P-H bond is added across a C-X multiple bond (X = C, N, O), as reviewed recently [3][4][5][6][7]. Scheme 1 shows a typical reaction of a terminal alkyne, showing the two possible regiochemical outcomes.…”