(E)-1,1,1-trifluoro-4-phenyl-but-2-ene-4-one and trimethyl phosphite

“On‐Water” Synthesis of Sterically Congested γ‐Ketophosphine Oxides Featuring a CF3‐ and P(O)‐Tetrasubstituted Carbon Center

“…Previously, Roeschenthaler et al . described a sole example of phosphonation at the β‐position of 1,1,1‐trifluoro‐4‐phenyl‐but‐2‐ene‐4‐one through a two‐step procedure for two days (Scheme 1, C) [11] . In 2022, Couve‐Bonnaire and co‐workers demonstrated the first phospha‐Michael addition on α‐fluoromethylacrylates, which led to new relevant structures containing both contiguous fluoroalkyl group and phosphorus moiety (Scheme 1, D) [12] .…”

“…[8c,17,18] Based on the above studies and literature survey, we propose a reaction mechanism for the "on-water" synthesis of sterically congested γ-ketophosphine oxides (Scheme 4). [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] Under basic reaction conditions, the diarylphosphinite anion A, generated in situ from diarylphosphine oxide 2, reacts with the β-CF 3β,β-disubstituted enone 1 through a classic 1,4-addition process, resulting in the formation of the β-phosphorylated anion B. During this step, the water surface presents hydrogen-bonding interactions that activate both substrates.…”

β‐Trifluoromethyl α,β‐unsaturated Ketones: Efficient Building Blocks for Diverse Trifluoromethylated Molecules

“…The reaction undergoes via [4 + 1] cycloaddition reaction, where the initial attack of phosphorus occurs at the β-carbon atom with subsequent ring closure producing 1,2λ 5 -oxaphospholene product B which upon hydrolysis delivers the fluo- roalkyl containing γ-ketophosphonate compound 111 (Scheme 32). [67]…”

The Phospha‐Michael Addition in Organic Synthesis

“…In the light of the preceeding discussion further comments are regarded unnecessary at this point, and the reader is referred to the cited references. [41][42][43] In the case of trivalent phosphorus nucleophiles of the general structure R 2 PORЈ only those compounds in which RЈ represents an alkyl or an aryl group have been under consideration so far. Although generally only 1,4-addition is observed with these compounds, the addition reactions are mostly sluggish at ambient temperature and do often require extensive heating.…”