A unified strategy for cobalt-catalyzed ortho-C-H bond alkynylation of benzylamines is reported. Simple, commercially available CoBr was used as a cobalt source. The developed alkynylation strategy is robust and efficient and has a broad substrate scope including 1°, 2°, and 3° benzylamines. The mechanistic study shows that C-H bond cleavage is reversible, and the kinetic study illustrates that the rate of reaction depends solely on the catalyst.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.6b02549 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cobalt-Catalyzed Divergence in C(sp)-H Functionalization of 9-Fluorene: A Streamlined Approach Utilizing Alcohols.
J Org Chem
October 2024
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517507, India.
Sustainable chemical production demands the creation of innovative catalysts and catalytic technologies. While the development of coherent and robust catalytic systems using earth-abundant transition metals is essential, it remains a significant challenge. Herein, an expedient divergence strategy for tandem dehydrogenative C(sp)-H alkylation and cyclization reactions of 9-fluorene using a newly developed ,-bidentate cobalt catalytic system is developed.
View Article and Find Full Text PDFCatalytic Asymmetric Barbier Reaction of Ketones with Unactivated Alkyl Electrophiles.
J Am Chem Soc
October 2024
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, China.
Article Synopsis
- The Barbier reaction is a method for adding aldehydes or ketones to organic electrophiles, forming carbon-carbon bonds without needing moisture-sensitive reagents.* -
- This study introduces a new photoredox-assisted cobalt-catalyzed version of the Barbier reaction, addressing challenges in creating complex chiral tertiary alcohols using unactivated alkyl electrophiles.* -
- The process can use various alkyl halides and redox-active esters, leading to diverse enantioenriched products, and demonstrates its effectiveness by synthesizing a core structure of a recently FDA-approved drug from 2024.*
A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition.
J Am Chem Soc
September 2024
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China.
Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications in biochemistry, medicinal chemistry, and materials science. Herein, we report a cobalt-catalyzed aza-Barbier reaction of dehydroglycines with unactivated alkyl halides to afford unnatural α-amino esters with high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use of moisture-, air-sensitive organometallic reagents, and stoichiometric chiral auxiliaries, enabling the conversion of a variety of primary, secondary, and even tertiary unactivated alkyl halides to α-alkyl-amino esters under mild conditions, thus leading to broad functional group tolerance.
View Article and Find Full Text PDFCobaltaelectro-Catalyzed C-H Activation for Central and Axial Double Enantio-Induction.
Angew Chem Int Ed Engl
July 2024
Institut für Organische und Biomolekulare Chemie, Wöhler-Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.
In recent years, enantioselective electrocatalysis has surfaced as an increasingly-effective platform for sustainable molecular synthesis. Despite indisputable progress, strategies that allow the control of two distinct stereogenic elements with high selectivity remain elusive. In contrast, we, herein, describe electrochemical cobalt-catalyzed C-H activations that enable the installation of chiral stereogenic centers along with a chiral axis with high levels of enantio- and diastereoselectivities.
View Article and Find Full Text PDFCobalt-Catalyzed Enantioselective Reductive α-Chloro-Carbonyl Addition of Ketimine to Construct the β-Tertiary Amino Acid Analogues.
Angew Chem Int Ed Engl
June 2024
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
β-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, the efficient asymmetric synthesis of this motif still remains a significant challenge. Herein, we disclose a cobalt-catalyzed enantioselective reductive addition reaction of ketimine using α-chloro carbonyl compound as a radical precursor, providing expedient access to a diverse array of enantioenriched β-quaternary amino acid analogues.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!