Isomerization of Aziridines to Allyl Amines via Titanium and Chromium Cooperative Catalysis.

J Org Chem

Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, United States.

Published: April 2022

A Ti/Cr cooperative catalyst isomerizes aziridines to allyl amines under mild conditions. The reaction tolerates a broad range of aziridines with various nitrogen substituents. The titanium catalyst is most successful in opening 1,2-disubstituted aziridines, forming radical intermediates in a highly regioselective manner. The chromium catalyst appears to abstract an H from these radical intermediates and then return the H to the titanium system in the form of an H and an electron. The reaction is complementary to previous reports on the isomerization of aziridines to allyl amines.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.joc.1c03054DOI Listing

Publication Analysis

Top Keywords

aziridines allyl
12
allyl amines
12
isomerization aziridines
8
radical intermediates
8
amines titanium
4
titanium chromium
4
chromium cooperative
4
cooperative catalysis
4
catalysis ti/cr
4
ti/cr cooperative
4

Similar Publications

Dynamic Kinetic Activation of Aziridines Enables Radical-Polar Crossover (4 + 3) Cycloaddition with 1,3-Dienes.

J Am Chem Soc

January 2025

State Key Laboratory of Applied Organic Chemistry & College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.

The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process is predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity of the C-N bond cleavage. In this study, we report a nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled activation of aziridines.

View Article and Find Full Text PDF

Regio-, Site- and Stereo-Selective Aziridination of Conjugated Dienes Enabled by Palladium/Copper/Iodide/Oxygen Cooperation.

Chemistry

January 2025

Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.

Vinylaziridines are important building blocks in organic chemistry, especially in the synthesis of nitrogen-containing heterocycles. The direct and efficient transfer of an appropriate nitrogen source to readily accessible conjugated dienes is a notable methodology. The Pd-catalyzed oxidative 1,2-difunctionalization of conjugated dienes through a π-allyl-palladium species should be an ideal method for the selective synthesis of vinylaziridines.

View Article and Find Full Text PDF

This work describes highly enantioselective nitrene transfer to hydrocinnamyl alcohols (benzylic C-H amination) and allylic alcohols (aziridination) using ion-paired Rh (II,II) complexes based on anionic variants of Du Bois' esp ligand that are associated with cinchona alkaloid-derived chiral cations. Directed by a substrate hydroxyl group, our previous work with these complexes had not been able to achieve high enantioselectivity on these most useful short-chain compounds, and we overcame this challenge through a combination of catalyst design and modified conditions. A hypothesis that modulation of the linker between the anionic sulfonate group and the central arene spacer might provide a better fit for shorter chain length substrates led to the development of a new biaryl-containing scaffold, which has allowed a broad scope for both substrate classes to be realized for the first time.

View Article and Find Full Text PDF

Catalytic asymmetric synthesis of 1,2-diamines.

Chem Soc Rev

July 2024

Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain.

The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, especially in the last ten years, due to their presence in biologically active compounds and their applications for the development of synthetic building blocks, chiral ligands and organocatalysts. Synthetic strategies based on C-N bond-forming reactions involve mainly (a) ring opening of aziridines and azabenzonorbornadienes, (b) hydroamination of allylic amines, (c) hydroamination of enamines and (d) diamination of olefins. In the case of C-C bond-forming reactions are included (a) the aza-Mannich reaction of imino esters, imino nitriles, azlactones, isocyano acetates, and isothiocyanates with imines, (b) the aza-Henry reaction of nitroalkanes with imines, (c) imine-imine coupling reactions, and (d) reductive coupling of enamines with imines, and (e) [3+2] cycloaddition with imines.

View Article and Find Full Text PDF
Article Synopsis
  • Metal-organic frameworks (MOFs) have great potential for various applications due to their versatile physical and chemical properties.
  • Traditional methods for synthesizing MOFs often involve harsh conditions that can degrade sensitive materials, such as Pd(ii), making it challenging to incorporate this metal into MOFs effectively.
  • The authors present a new mechanochemical approach that allows for the integration of Pd(ii)-based clusters into MOFs without reducing Pd(ii), highlighting benefits like shorter reaction times, minimal solvent use, and improved control over the synthesis process.
View Article and Find Full Text PDF

Want 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!