Manganese-Catalyzed Oxophosphorylation Reaction of Carbon–Carbon Double Bonds Using Molecular Oxygen in Air

Abstract

A novel aerobic manganese-catalyzed oxophosphorylation reaction of carbon-carbon double bonds of styrene derivatives and vinyl ethers using diethyl H-phosphonates was developed. This direct transformation of alkenes to β-ketophosphonate readily proceeded at room temperature via the direct incorporation of molecular oxygen present in air (open flask).

Iron‐Catalyzed Oxyphosphorylation of Styrenes to Access β‐Ketophosphonates and α, β‐Unsaturated Ketones

“…Meanwhile, Chen and Zhao [8] found that the single copper salt could catalyze the oxophosphorylation reaction of α , β ‐alkenyl carboxylic acids or styrenes with H‐phosphonates under air atmosphere. Also, Makino group [9] realized such catalytic process at room temperature by using Mn(acac) 3 as a catalyst. Although these difunctionalization protocols allowed the construction of β ‐ketophosphonates from readily available starting materials, they usually relied on the catalytic activity of copper or manganese metals.…”

Recent trends in the direct oxyphosphorylation of C–C multiple bonds

“…Afterwards, Yamamoto–Makino's group extended the scope of alkenes to vinyl ethers. 24 Thus, several alkyl/aryl 2-(diethoxyphosphoryl)acetates 21 were synthesized in moderate yields, ranging from 42% to 57%, via the Mn(acac) 3 -catalyzed oxyphosphorylation of corresponding vinyl ethers 19 with dimethyl phosphonate 20 and O 2 in MeCN at room temperature ( Scheme 8 ). Noteworthy, Mn(acac) 2 was also found to promote this transformation; albeit, at lower efficiency.…”