Hydrophosphorylations rhodium

Hydrophosphorylation has recently been extended to rhodium catalysts as a route to anti-Markovnikoff products.198 Thus, 3mol.% Rh(PPh3)3Cl affords the ( )-alkenylphosphonates (R = H, Ph, -Cr,I I ]3, CH2CH2CN, SiMe3, or cyclohexenyl) in high yields (>80%) at room temperature when 4,4,5,5-tetramethyl-l,3,2-dioxaphospholane-2-oxide (74) is used as the PH source (Equation (19)).199 The rate of reaction is highly solvent dependent... 

Addition to olefins has not made an epoch-making progress since the publicatirais on hydrophosphorylation using pinacol phosphonate [50] and unsubstituted phosphinic acid (hypophosphorous acid) derivatives [25], inclusive of the extension to rhodium-catalyzed reactions of pinacol phosphonate [51]. No publication has appeared to disclose addition reactions of a phosphine oxide except for cyclopropenes (vide infra). 

Zhao Ch-Q, Han L-B, Goto M, Tanaka M (2001) Rhodium-catalyzed hydrophosphorylation of terminal alkynes leading to highly selective formation of (i )-afkenylphosphonates complete reversal of regioselectivity to the palladium-catalyzed counterpart. Angew Chem Int Ed 40 1929-1932... 

Reichwein JF, Patel MC, Pagenkopf BL (2001) Rhodium-catalyzed regioselective olefin hydrophosphorylation. Org Lett 3 4303-4306... 

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