The mechanisms of the α-, β- and γ-functionalisations of aldehydes and α,β-unsaturated aldehydes by secondary amines are presented and discussed.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c0cc02417a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Understanding the Diastereopreference of Intermediates in Aminocatalysis: Application to the Chiral Resolution of Lactols.
J Org Chem
March 2021
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Downstream intermediates are crucial for the reactivity and selectivity of aminocatalytic reactions. We present an analysis of the stereopreference in aminocatalytic downstream intermediates, which reveals an inconspicuous mechanism of chiral recognition between the catalyst and the rest of the molecule. We delineate a stereoelectronic model to rationalize the mode of chiral transmission.
View Article and Find Full Text PDFC Kinetic Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine Mechanisms in Aminocatalysis.
Chemistry
June 2018
Department of Chemistry, Binghamton University, Binghamton, NY, 13902, USA.
A combination of experimental C kinetic isotope effects (KIEs) and high-level density functional theory (DFT) calculations is used to distinguish between "enamine" and "enol" mechanisms in the Michael addition of acetone to trans-β-nitrostyrene catalyzed by Jacobsen's primary amine thiourea catalyst. In light of the recent findings that the widely used O-incorporation probe for these mechanisms is flawed, the results described in this communication demonstrate an alternative probe to distinguish between these pathways. A key advantage of this probe is that quantitative mechanistic information is obtained without modifying experimental conditions.
View Article and Find Full Text PDFEnantioselective Decarboxylative α-Alkynylation of β-Ketocarbonyls via a Catalytic α-Imino Radical Intermediate.
Org Lett
September 2017
Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.
A distinctive aminocatalysis via α-imino radical is reported on the basis of SET oxidation of a secondary enamine. The combination of chiral primary amine catalysis and visible-light photoredox catalysis enables the enantioselective decarboxylative coupling of propiolic acid and β-ketocarbonyls to afford alkynylation adducts with high enantioselectivity. Mechanism studies indicate the reaction proceeds via an α-imino radical addition.
View Article and Find Full Text PDFDouble Activation Catalysis for α'-Alkylidene Cyclic Enones with Chiral Amines and Thiols.
Chemistry
August 2017
Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, P. R. China.
Cooperative catalysis has contributed greatly to the progress of asymmetric synthesis. However, double-activation catalysis has been less explored, especially for covalently tethered species. Here, we present a double-activation strategy for α'-alkylidene cyclic enone substrates that uses a chiral primary amine and 2-mercaptobenzoic acid to promote regio- and chemoselective addition to generate the complex interrupted iminium ion species.
View Article and Find Full Text PDFComputational Approach to Diarylprolinol-Silyl Ethers in Aminocatalysis.
Acc Chem Res
May 2016
Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
Asymmetric organocatalysis has witnessed a remarkable development since its "re-birth" in the beginning of the millenium. In this rapidly growing field, computational investigations have proven to be an important contribution for the elucidation of mechanisms and rationalizations of the stereochemical outcomes of many of the reaction concepts developed. The improved understanding of mechanistic details has facilitated the further advancement of the field.
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!