Calcium-catalyzed diastereo- and enantioselective 1,4-addition of glycine derivatives to alpha,beta-unsaturated esters.

Org Lett

Department of Chemistry, School of Science and Graduate School of Pharmaceutical Sciences, The University of Tokyo, The HFRE Division, ERATO, Japan Science Technology Agency, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

Published: March 2008

The first highly diastereo- and enantioselective catalytic asymmetric 1,4-addition reactions of a glycine Schiff base to beta-substituted alpha,beta-unsaturated esters have been developed. The reaction pathway was successfully controlled, and the desired 1,4-addition products were exclusively obtained with high enantioselectivities. The product obtained was converted to a 3-substituted glutamic acid derivative by acid hydrolysis.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ol702958wDOI Listing

Publication Analysis

Top Keywords

diastereo- enantioselective
8
alphabeta-unsaturated esters
8
calcium-catalyzed diastereo-
4
enantioselective 14-addition
4
14-addition glycine
4
glycine derivatives
4
derivatives alphabeta-unsaturated
4
esters highly
4
highly diastereo-
4
enantioselective catalytic
4

Similar Publications

Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters.

J Am Chem Soc

January 2025

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

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration of cyclopropenes, with less reactive alkyl iodides as electrophiles, for the efficient synthesis of -substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, a broad substrate scope, and good functional group tolerance, affording an array of chiral borylated cyclopropanes in good to high yields with excellent diastereo- and enantioselectivities.

View Article and Find Full Text PDF

Amide-Directed Highly Enantioselective Hydrogenation of Diverse Acyclic Multisubstituted Alkenes Under Mild Conditions.

Angew Chem Int Ed Engl

January 2025

Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.

Enantioselective hydrogenation of tetrasubstituted alkenes to form 1,2-contiguous stereocenters is a particularly appealing but highly challenging transformation in asymmetric catalysis. Despite the notable progress achieved in enantioselective hydrogenation over the past decades, enantioselective hydrogenation of all-carbon tetrasubstituted alkenes containing multiple alkyl groups remains an unsolved challenge. Here, we report a rhodium-catalyzed highly diastereo- and enantioselective hydrogenation of diverse acyclic multisubstituted alkenes under mild conditions.

View Article and Find Full Text PDF

Nozaki-Hiyama-Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, the application of multicomponent NHK-type reactions, which allow the formation of multiple bonds in a single step, has been largely restricted to bulky alkyl radical precursors, thus limiting their expanded utilization. Herein, we disclose a general three-component NHK-type reaction enabled by delayed radical-polar crossover, which efficiently tolerates a plethora of radical precursors that were previously unavailable.

View Article and Find Full Text PDF

A highly regio-, enantio- and diastereo-selective strategy involving initial enantioselective conjugate addition to 4-nitro-5-styrylisoxazoles serves as a key step for the desymmetrization of 2,5-cyclohexadienones has been disclosed. We have designed a new class of 2,5-cyclohexadienones appended with 4-nitro-5-styrylisoxazoles to undergo organocatalytic asymmetric double or triple conjugate addition in a domino sequence depending on the substrate type leading to desymmetrization of the 2,5-cyclohexadienone core. The developed protocol allows the construction of a valuable hydrophenanthrene core or a unique bridged scaffold bearing multiple chiral centers with excellent enantio- (up to >99.

View Article and Find Full Text PDF

Photoredox/Cobalt-Catalyzed Chemo-, Regio-, Diastereo- and Enantioselective Reductive Coupling of 1,1-Disubstituted Allenes and Cyclobutenes.

Angew Chem Int Ed Engl

December 2024

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.

A dual photoredox/cobalt-catalyzed protocol for chemo-, regio-, diastereo- and enantioselective reductive coupling of 1,1-disubstituted allenes and cyclobutenes through chemo-, regio-, diastereo- and enantioselective oxidative cyclization followed by stereoselective protonation promoted by a chiral phosphine-cobalt complex is presented. Such process represents an unprecedented reaction pathway for cobalt catalysis that enables selective transformation of the less sterically congested alkenes of 1,1-disubstituted allenes with cyclobutenes, incorporating a broad scope of tetrasubstituted alkenes into the cyclobutane scaffolds in up to 86 % yield, >98 : 2 chemo- and regioselectivity, >98 : 2 dr and >99.5:0.

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!