Effects of B2pin2 and PCy3 on copper-catalyzed trifluoromethylation of substituted alkenes and alkynes with the Togni reagent

Copper-Catalyzed C(sp2)–H Difluoroalkylation of Aldehyde Derived Hydrazones with Diboron as Reductant

“…On the basis of the above control experiments, our previous work, and preceding reports, a plausible mechanism is postulated (Figure ). Initially, interaction between the Cu­(II) salt A and B 2 pin 2 generates the Cu I /Bpin species B . ,, Subsequently, an electrophilic fluoroalkyl radical from bromodifluoro reagent is formed via bromide abstraction by the copper­(I) complex B with concomitant generation of copper­(II) C . , The radical can be trapped by aldehyde derived hydrazone to form the aminyl radical D , which further converts into intermediate E via an SET process. , Then the removal of a proton eventually produces the desired product 3 .…”

Catalytic Intramolecular Aminofluorination, Oxyfluorination, and Carbofluorination with a Stable and Versatile Hypervalent Fluoroiodine Reagent

“…[ 2b , d , e ] We expected that conceptual analogies between 1 and its CF 3 analogue could be exploited for the development of new catalytic fluorination reactions. For example, catalytic oxytrifluoromethylation[ 11c , d , 13 ] and aminotrifluoromethylation[ 14 ] with the Togni reagent are well-known methods, and therefore it was appealing to attempt oxyfluorination and aminofluorination reactions with 1 . Furthermore, unlike Ar-IF 2 derivatives, 1 is a stable and easily accessible reagent,[ 15 ] which is a potent oxidant, a fluorine source, and a preformed base in one reagent.…”

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

“…The group of Szabó has first reported the use of copper(I) iodide as a catalyst for the regioselective difunctionalization of aromatic alkynes and alkenes with an optimal atom-economy ( Scheme 4 ) [ 34 – 35 ]. The transformation proceeds efficiently, particularly in the presence of an electron-donating substituent on the aromatic ring.…”

“…The mechanistic study of the oxy-trifluoromethylation of phenylacetylene has then led to demonstrate that the reaction is accelerated in the presence of additives such as B 2 pin 2 [ 35 ]. A mechanism involving an initial step of transmetallation of B 2 pin 2 with the Cu(I) catalyst was proposed ( Scheme 4 ).…”