4 research outputs found
Designing New Magnesium Pincer Complexes for Catalytic Hydrogenation of Imines and <i>N</i>‑Heteroarenes: H<sub>2</sub> and N–H Activation by Metal–Ligand Cooperation as Key Steps
Utilization of main-group
metals as alternatives to transition
metals in homogeneous catalysis has become a hot research area in
recent years. However, their application in catalytic hydrogenation
is less common due to the difficulty in heterolytic cleavage of the
H–H bond. Employing aromatization/de-aromatization metal–ligand
cooperation (MLC) highly enhances the H2 activation process,
offering an efficient approach for the hydrogenation of unsaturated
molecules catalyzed by main-group metals. Herein, we report a series
of new magnesium pincer complexes prepared using PNNH-type pincer
ligands. The complexes were characterized by NMR and X-ray single-crystal
diffraction. Reversible activation of H2 and N–H
bonds by MLC employing these pincer complexes was developed. Using
the new magnesium complexes, homogeneously catalyzed hydrogenation
of aldimines and ketimines was achieved, affording secondary amines
in excellent yields. Control experiments and DFT studies reveal that
a pathway involving MLC is favorable for the hydrogenation reactions.
Moreover, the efficient catalysis was extended to the selective hydrogenation
of quinolines and other N-heteroarenes, presenting
the first example of hydrogenation of N-heteroarenes
homogeneously catalyzed by early main-group metal complexes. This
study provides a new strategy for hydrogenation of CN bonds
catalyzed by magnesium compounds and enriches the research of main-group
metal catalysis
Chiral Selenide-Catalyzed Enantioselective Allylic Reaction and Intermolecular Difunctionalization of Alkenes: Efficient Construction of C‑SCF<sub>3</sub> Stereogenic Molecules
New
approaches for the synthesis of enantiopure trifluoroÂmethylÂthiolated
molecules by chiral selenide-catalyzed allylic trifluoroÂmethylÂthiolation
and interÂmolecular difunctionalization of unactivated alkenes
are disclosed. In these transformations, functional groups were well
tolerated, and the desired products were obtained in good yields with
excellent chemo-, enantio-, and diastereoÂselectivities. This
reaction is nicely complementary to enantioÂselective trifluoroÂmethylÂthiolation,
allylic functionalization, and interÂmolecular alkene difunctionalization
Chiral Selenide-Catalyzed Enantioselective Allylic Reaction and Intermolecular Difunctionalization of Alkenes: Efficient Construction of C‑SCF<sub>3</sub> Stereogenic Molecules
New
approaches for the synthesis of enantiopure trifluoroÂmethylÂthiolated
molecules by chiral selenide-catalyzed allylic trifluoroÂmethylÂthiolation
and interÂmolecular difunctionalization of unactivated alkenes
are disclosed. In these transformations, functional groups were well
tolerated, and the desired products were obtained in good yields with
excellent chemo-, enantio-, and diastereoÂselectivities. This
reaction is nicely complementary to enantioÂselective trifluoroÂmethylÂthiolation,
allylic functionalization, and interÂmolecular alkene difunctionalization
Chiral Selenide-Catalyzed Enantioselective Allylic Reaction and Intermolecular Difunctionalization of Alkenes: Efficient Construction of C‑SCF<sub>3</sub> Stereogenic Molecules
New
approaches for the synthesis of enantiopure trifluoroÂmethylÂthiolated
molecules by chiral selenide-catalyzed allylic trifluoroÂmethylÂthiolation
and interÂmolecular difunctionalization of unactivated alkenes
are disclosed. In these transformations, functional groups were well
tolerated, and the desired products were obtained in good yields with
excellent chemo-, enantio-, and diastereoÂselectivities. This
reaction is nicely complementary to enantioÂselective trifluoroÂmethylÂthiolation,
allylic functionalization, and interÂmolecular alkene difunctionalization