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

Abstract

The distinctive hydrophobic hydration effect in the aqueous solution contributes to the success of the phospha‐Michael reaction between β‐CF3‐β,β‐disubstituted enones and diarylphosphine oxides, providing an access to biologically relevant γ‐ketophosphine oxides bearing a sterically highly congested CF3‐ and P(O)‐tetrasubstituted carbon center. More importantly, the resulting products could be further transformed into densely functionalized γ‐ketophosphine oxides containing a CF3‐ and P(O)‐tetrasubstituted carbon center.

Water-promoted defluorinative synthesis of fluoroalkylated 1,5-diazapentadienes by using (NH4)2CO3 as an NH2 and NH source

“…1C). 16,17 As a continuation of our research efforts in defluorination reactions, 18 herein we describe a H 2 O-promoted and (NH 4 ) 2 CO 3 -enabled defluorination of fluoroalkyl alkenes under transition-metal-free conditions (Fig. 1D).…”

“…On the basis of the abovementioned experimental observations and previous literature, 14–22 two possible reaction mechanisms for the H 2 O-promoted and (NH 4 ) 2 CO 3 -enabled deiodoamination-defluoroiminization cascade of perfluoroalkyl alkenes is proposed in Scheme 3. Initially, perfluoroalkyl alkene 1 readily undergoes S N V-type C(sp 2 )–I bond displacement with a molecule of NH 3 to generate enamine B .…”