om0c00233_si_001.pdf (4.67 MB)
Solvent-Free N‑Alkylation and Dehydrogenative Coupling Catalyzed by a Highly Active Pincer-Nickel Complex
journal contribution
posted on 2020-05-22, 19:15 authored by Vinay Arora, Moumita Dutta, Kanu Das, Babulal Das, Hemant Kumar Srivastava, Akshai KumarThe
synthesis and characterization of a pincer-nickel complex of
the type (iPr2NNN)NiCl2(CH3CN) is reported here. We have demonstrated the utility of
this pincer-nickel complex (0.02 and 0.002 mol %) for the catalytic
N-alkylation of amines using various alcohols. Under solvent-free
conditions, while the highest yield (ca. 90%) was obtained for the
alkylation of 2-aminopyridine with naphthyl-1-methanol, excellent
turnovers (34000 TONs) were observed for the alkylation of 2-aminopyridine
with 4-methoxybenzyl alcohol. To demonstrate the synthetic utility
of these systems, high-yield reactions (up to 98%) have been probed
for representative substrates with a higher loading of the pincer-nickel
catalyst (4 mol %). DFT studies indicate that while β-hydride
elimination is the RDS for alcohol dehydrogenation, the N-alkylated
product can be formed either via hydrogenation with a rate-determining
σ-bond metathesis or by alcoholysis that has imine insertion
as the RDS. All of the corresponding resting states have been observed
by HRMS (ESI) analysis. The labeling experiments are also complementary
to DFT studies and show evidence for the involvement of the benzylic
C–H bond in the RDS with a kCHH/kCHD value of about 2.5. This method
has been applied to accomplish efficient (2000 TONs) dehydrogenative
coupling leading to various benzimidazoles.