Palladium catalyzed Suzuki cross-coupling of benzyltrimethylammonium salts via C–N bond cleavage

Abstract

A Pd catalyzed Suzuki cross-coupling of a benzyltrimethylammonium salt is described. This reaction offers a highly efficient approach to diarylmethanes and also paves the way for the application of benzyltrimethylammonium salts in Pd catalyzed cross-coupling reactions.

Synthesis of Arylethylamines via C(sp3)–C(sp3) Palladium-Catalyzed Cross-Coupling

“…Thus, on the basis of previous reports, − a plausible mechanism (Scheme ) involves oxidative addition of betaine 4 , generated in situ , to the active Pd(0) catalyst A . Upon this oxidative addition to form Pd­(II) species B , the dialkylaminomethyltrifluoroborate salt may be liberated prior to hydrolysis to the boronic acid 5 , in accordance with mechanisms reported by Lloyd-Jones and co-workers. , Ligand exchange and transmetalation afford complex C , from which reductive elimination furnishes the desired arylethylamine 3 .…”

Recent Advances in the Pd‐Catalyzed Coupling of Arylhydrazines and Ammonium Salts via C−N Bond Cleavage

“…In 2017, our group described the first Pd-catalyzed crosscoupling reaction of benzyl ammonium salts with boronic acids via CÀ N bond cleavage (Scheme 24). [38] It should be noted that the ligand is vital for this process; the product could be obtained in 67 % yield using PPh 3 as a ligand. Surprisingly, the homocoupling of boronic acid could be suppressed and coupling products obtained in up to 98 % yield when ethanol was used as the solvent.…”

Ni-Catalyzed C–P Coupling of Aryl, Benzyl, or Allyl Ammonium Salts with P(O)H Compounds

“…Organoammonium salts as readily accessible and stable coupling substrates for C–C and C–heteroatom bond construction were reported by us and other groups. , For example, nickel-catalyzed reaction of aryl- and benzyltrimethyl­ammonium salts with B 2 pin 2 afforded organoboronates via the C–N bond cleavage . Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates with amines resulted in the formation of new aromatic amines .…”