A Comparative Reactivity Survey of Some Prominent Bisphosphine Nickel(II) Precatalysts in C-N Cross-Coupling

作者：Clark Jillian S K; Lavoie Christopher M; MacQueen Preston M; Ferguson Michael J; Stradiotto Mark

来源：Organometallics, 2016, 35(18): 3248-3254.

DOI：10.1021/acs.organomet.6b00650

The synthesis and characterization of the new air-stable precatalyst (L1)Ni(o-tol)Cl (Cl; where L1 = JosiPhos CyPF-Cy) is reported, along with the results of a comparative reactivity survey involving Cl and analogous PAd-DalPhos- and DPPF-containing precatalysts (C2 and C3, respectively) in representative nickel-catalyzed C(sp(2))-N cross-coupling reactions. Precatalyst C1 was found to be competitive with, and in some cases complementary to, C2 in the monoarylation of ammonia and primary alkylamines with (hetero)aryl chlorides, including in otherwise challenging room temperature transformations. (Pseudo)halide comparison studies involving the cross-coupling of furfurylamine at room temperature revealed that in contrast to C2 precatalyst Cl performs less effectively with aryl bromides. Whereas C3 was found to be ineffective for such transformations, this DPPF-derived precatalyst proved superior to C1 and C2 in reactions involving the secondary dialkylamine test substrate morpholine.

• 出版日期2016-9-26