Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
The efficient synthesis of chiral amines has garnered ongoing interest due to their prevalence in pharmaceuticals and biologically active compounds. However, most existing strategies for their synthesis primarily rely on asymmetric (transfer) hydrogenation (AH/ATH) using noble metal catalysts. Additionally, the AH/ATH of heteroatom-containing imines and diarylimines has posed a longstanding challenge. In this study, we have developed a general method for the ATH of heteroatom-containing imines and diarylimines, catalyzed by a chiral aminobenzimidazole manganese(I) complex, yielding the corresponding amines in up to 99% yield and 99% ee. Furthermore, the reaction proceeds smoothly on a gram scale without any loss of enantioselectivity, indicating its potential applicability in the synthesis of important pharmaceuticals. Based on deuterium labeling and control experiments, we also propose a possible mechanism for this manganese(I)-catalyzed ATH of imines with NH·BH.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.5c08335 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Manganese-Catalyzed Asymmetric Transfer Hydrogenation of Heteroatom-Containing Imines and Diarylimines.
J Am Chem Soc
August 2025
State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
The efficient synthesis of chiral amines has garnered ongoing interest due to their prevalence in pharmaceuticals and biologically active compounds. However, most existing strategies for their synthesis primarily rely on asymmetric (transfer) hydrogenation (AH/ATH) using noble metal catalysts. Additionally, the AH/ATH of heteroatom-containing imines and diarylimines has posed a longstanding challenge.
View Article and Find Full Text PDFAccessing Functionalized Ultra-High Molecular Weight Poly(α-olefin)s via Hafnium-Mediated Highly Isospecific Copolymerization.
Macromol Rapid Commun
August 2024
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun, 130022, China.
Inspired by the favorable impact of heteroatom-containing groups in phenoxy-imine titanium and late transition metal catalysts, a series of novel pyridylamido hafnium catalysts bearing ─OMe (Cat-OMe), ─CF (Cat-CF), and ─CF (Cat-CF) substituents are designed and synthesized. Together with the established hafnium catalysts Cat-H and Cat-iPr by Dow/Symyx, these catalysts are applied in the polymerization of α-olefins, including 1-hexene, 1-octene, and 4M1P, as well as in the copolymerization of these α-olefins with a specifically designed polar monomer. The enhancement of polymer molecular weight derived from catalyst modification and the incorporation of polar monomers is discussed in detail.
View Article and Find Full Text PDFTuning Photoenolization-Driven Cycloadditions Using Theory and Spectroscopy.
J Am Chem Soc
January 2022
Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia.
The first broad spectrum investigation into the photoenolization/Diels-Alder (PEDA) sequence was carried out using M06-2X/6-31+G(d,p) in conjunction with SMD solvation and supported by experimental UV-vis spectroscopy. A test set of 20 prodienes was chosen to examine the role of the H atom acceptor group (substituted and unsubstituted carbonyl, thiocarbonyl, and imine), the H atom donor group, and bystander ring substituents. As reaction partners for the photogenerated dienes, a diverse test set of 20 dienophiles was examined, comprising electron rich, electron poor, neutral, strain activated, hydrocarbon, and heteroatom-containing molecules including CO and CO.
View Article and Find Full Text PDFConjugated Ynones in Organic Synthesis.
Chem Rev
October 2019
Centro de Innovación en Química Avanzada (ORFEO-CINQA) , Universidad de Alicante , Apdo. 99 , Alicante E-03080 , Spain.
This review article will consider the preparation and application of ynones in synthetic organic chemistry. Concerning the preparation of these bifunctional compounds, several methodologies starting from propargyl alcohols, acyl derivatives, both by using alkynylmetal reagents or by transition metal (mainly palladium and copper) catalyzed alkynylations, carbon monoxide (carbonylation of terminal alkynes and alkenes), and other substrates will be discussed. The reactivity and synthetic applications of ynones will be focused on conjugate additions with boron-, carbon-, nitrogen-, oxygen-, and other heteroatom-containing nucleophiles, as well as radicals.
View Article and Find Full Text PDFRapid, Low Temperature Formation of Imine-Linked Covalent Organic Frameworks Catalyzed by Metal Triflates.
J Am Chem Soc
April 2017
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
Imine-linked two-dimensional covalent organic frameworks (2D COFs) are crystalline polymer networks with enhanced stability compared to boronate ester-linked systems and with broad monomer scope. They are traditionally prepared by condensing polyfunctional aldehydes and amines at elevated temperature in a mixture of organic solvents and aqueous CHCOH, which catalyzes imine formation and exchange. Here we employ metal triflates, which are water-tolerant Lewis acids, to accelerate 2D imine-linked COF synthesis and improve their materials quality.
View Article and Find Full Text PDF