Fluorine-controlled C–H borylation of arenes catalyzed by a PSiN-pincer platinum complex

Abstract

An efficient, regioselective synthesis of fluorine-substituted arylboronic esters was achieved through fluorine-controlled C-H borylation of arenes with diboron catalyzed by a PSiN-platinum complex. The promising utility of the PSiN-platinum catalyst and its unique regioselectivity were demonstrated for the first time, which would complement the well-developed Ir-catalyzed C-H borylation.

C(sp2)–H Borylation of Fluorinated Arenes Using an Air-Stable Cobalt Precatalyst: Electronically Enhanced Site Selectivity Enables Synthetic Opportunities

“…11 Alternative strategies for the preparation of single regioisomers of fluorinated aryl boronate esters have been developed, including installation and removal of blocking groups to increase the selectivity of the iridium-catalyzed reaction. 12 Use of NHC- 13a and PSiN-ligated platinum catalysts, 13b as well as phosphine- 14a and POP-supported rhodium catalysts, 14b have all been explored to increase the ortho -to-fluorine selectivity in fluoroarene borylation. While these were important advances, the requirement of excess arene, elevated temperatures, and multiple fluorines in the arene substrate detract from the general utility of these methods.…”

“…While these were important advances, the requirement of excess arene, elevated temperatures, and multiple fluorines in the arene substrate detract from the general utility of these methods. 13,14 …”

(N),C,N‐Coordinated Heavier Group 13–15 Compounds: Synthesis, Structure and Applications

“…These studies demonstrate the important role of the additional heteroatoms Y (Y=P, O) in the C,N ‐coordinated silanes, since the presence of the Y,Si ‐coordination has been postulated in both transition metal mediated catalytic cycles …”

“…It was also postulated, that the silane [Ar CN SiMe(C 6 H 4 ‐PCy 2 )]PtCl, with the P,Si,N ‐chelatation of the Pt atom, has been used as catalyst for C–H borylation of arenes. This method was controlled by the fluorine substituents and it provided series of fluorine‐substituted arylboronic esters (Scheme ), but chloroarenes or benzoate were studied experimentally as well …”

Versatile Silylphosphine Ligands for Transition Metal Complexation

“…The chemistry of mixed PSiN ligands[36][37].Versatile Silylphosphine Ligands for Transition Metal Complexation http://dx.doi.org/10.5772/intechopen.73502 (R = tBu (140); Cy (141); iPr (142); Ph (143)) [36]. The complexes [PtCl{(ο-C 6 H 4 )-PR 2 (ο-C 6 H 4 )-NMe 2 -SiMe}] (R = tBu (145); Cy (151); iPr (152); Ph (153)) were synthesised by the reaction with [PtCl 2 η 2 -(C 2 H 4 )] 2 in the presence of Et 3 N. In particular, the PSiN-platinum complex 151 successfully catalysed C─H borylation not only of highly electron deficient perfluoroarenes but also of the monofluorinated arenes, chloroarenes and benzoate (Figure 10) [37].…”