Palladium/Copper Dual Catalysis for the Cross‐Coupling of Aryl(trialkyl)silanes with Aryl Bromides

Abstract

Whereas aryl(trialkyl)silanes are considered to be ideal organometallic reagents for cross-coupling reactions owing to their stability, low toxicity, solubility, and easy accessibility, they are generally inert under typical cross-coupling conditions. Disclosed herein is a palladium/copper catalytic system that enables the cross-coupling of trimethyl, triethyl, tert-butyldimethyl, and triisopropyl aryl silanes with aryl bromides. This process is applicable to the sequential C-H and C-Si bond arylation of thiophenes and the synthesis of poly(thiophene-fluorene)s.

Silver-catalyzed direct benzylation of acetanilide: a highly efficient approach to unsymmetrical triarylmethanes

“…The bromide substituted arenes can be further transformed into various other functional groups by well-known cross-coupling reactions. 24 Therefore, 2-bromoacetanilide was employed to investigate the scope of benzhydrol and the results were listed in Scheme 3 . The results clearly show that the functional groups, such as Me, F, Cl, Br, CF 3 , and Ph were all fully tolerated in this reaction.…”

The 2‐Pyridyl Problem: Challenging Nucleophiles in Cross‐Coupling Arylations

“…[60] Thes ame group subsequently reported ad ual Pd/Cu catalytic system which allowed the coupling of ar ange of silyl groups under milder conditions (Scheme 10, conditions B). [61] Thee fficiencyo ft hese couplings was demonstrated with al arge scope of heterocyclic substrates,aswell as challenging polyfluorocarbocyclic nucleophiles,but the pyridine scope was once again limited.…”

The 2‐Pyridyl Problem: Challenging Nucleophiles in Cross‐Coupling Arylations

“…The Hiyama group showed that 2‐pyridyltriethylsilanes could also be employed in a copper‐catalysed cross‐coupling reaction with aryl halides (Scheme 10, conditions A) [60] . The same group subsequently reported a dual Pd/Cu catalytic system which allowed the coupling of a range of silyl groups under milder conditions (Scheme 10, conditions B) [61] . The efficiency of these couplings was demonstrated with a large scope of heterocyclic substrates, as well as challenging polyfluorocarbocyclic nucleophiles, but the pyridine scope was once again limited.…”