Copper-catalyzed asymmetric direct alkynylation of α-ketoesters with terminal alkynes with chiral prolinol-phosphine ligands, most preferably (α,2)-1-(2-dicyclohexylphosphinobenzyl)-α-neopentyl-2-pyrrolidinemethanol, afforded various enantioenriched chiral propargylic tertiary alcohols. Quantum-chemical calculations using the BP86 density functional including Grimme's empirical dispersion correction [DF-BP86-D3(BJ)-PCM(BuOH)/TZVPP//DF-BP86-D3(BJ)/SVP] show the occurrence of OH···O/sp-CH···O two-point hydrogen bonding between the chiral ligand and the carbonyl group of the ketoester in the stereo-determining transition states. Combined with the hydrogen-bonding interactions orienting the ketoester substrate, dispersive attractions between the chiral ligand (-cyclohexyl groups) and the ketoester in the favored transition states, rather than steric repulsions in the disfavored transition state explain the enantioselectivity of the asymmetric copper catalysis.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5933290 | PMC |
| http://dx.doi.org/10.1039/c8sc00527c | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Stereocontrolled Synthesis of the Portimine Skeleton via Organocatalyst-Mediated Asymmetric Stannylation and Stereoretentive C()-C() Stille Coupling.
Org Lett
January 2025
Graduate School of Life Sciences, Tohoku University, 2-1-1 Katahira, 980-8577 Aoba-ku, Sendai, Japan.
Our efforts toward the synthesis of the marine natural product portimine are described. The key to the synthesis of the skeleton is a stereoretentive copper-catalyzed C()-C() Stille-type cross-coupling that enables the convergent assembly of functionalized fragments. The core skeleton of portimine was constructed via ring-closing metathesis and transannular acetal formation.
View Article and Find Full Text PDFDual Photoredox and Copper-Catalyzed Asymmetric Remote C(sp)-H Alkylation of Hydroxamic Acid Derivatives with Glycine Derivatives.
J Org Chem
January 2025
Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, Sichuan Engineering Laboratory for Plant-Sourced Drug and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.
Dual photoredox and copper-catalyzed remote asymmetric C(sp)-H alkylation of hydroxamic acid derivatives with glycine derivatives via a 1,5-hydrogen transfer (1,5-HAT) process has been realized. The reaction was characterized by redox-neutral and mild conditions, good yields, excellent enantioselectivity, and broad substrate scope. This protocol provides a straightforward and efficient strategy to prepare highly valuable enantioenriched noncanonical α-amino acids.
View Article and Find Full Text PDFCopper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines.
J Am Chem Soc
January 2025
State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
Article Synopsis
- The catalytic asymmetric transformation of donor-acceptor cyclopropanes (DACs) is an important method for creating a variety of enantioenriched molecules, but using tetrasubstituted DACs to generate products with quaternary stereocenters has been a persistent challenge.
- This study introduces a copper-catalyzed asymmetric aminative ring-opening process for tetrasubstituted alkynyl DACs that successfully produces a wide range of α-tertiary amines with high enantioselectivity.
- The resulting products, which contain alkyne, amine, and ester groups, open up new possibilities for synthesizing bioactive molecules, with mechanism studies highlighting the significance of a zwitter
Copper-Catalyzed Enantioselective Skeletal Editing through a Formal Nitrogen Insertion into Indoles to Synthesize Atropisomeric Aminoaryl Quinoxalines.
Angew Chem Int Ed Engl
December 2024
State key laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin, 541004, China.
Skeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown.
View Article and Find Full Text PDFEnantioselective Synthesis of Spirooxindole-Pyran and Furan Scaffolds via Copper-Catalyzed Formal (3+3) and (3+2) Cycloaddition of Isatin-Derived Propargylic Esters.
Chemistry
December 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, Kanpur, 208016, India.
Herein, we report a copper-catalyzed enantioselective formal (3+3) and (3+2) cycloaddition reaction of isatin-derived tertiary propargylic esters with N,N-dimethylbarbituric acid and 4-hydroxycoumarins, respectively. In this process, the tertiary propargylic ester serves as both C3- and C2-synthons, facilitating the synthesis of optically active spirooxindole-pyran and furan scaffolds featuring an all-carbon quaternary stereocenter. The reaction delivers these spirocyclic frameworks in good yields with high enantioselectivities.
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!