Enantioselective Propargylic C(sp)-H Acyloxylation Enabled by Photoexcited Copper Catalysis.

Org Lett

State Key Laboratory of Analytical Chemistry for Life Science, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.

Published: November 2024

Direct C-H bond functionalization is an efficient method for modifying organic molecules. However, achieving high enantioselectivity and regioselectivity in asymmetric C-H functionalization, particularly of C(sp)-H bonds, remains challenging. This study introduces an enantioselective propargylic C(sp)-H acyloxylation using photoexcited copper catalysis. The reaction demonstrated tolerance for various alkynes and peroxides, producing chiral propargyl esters in high yields and enantiomeric excess. Furthermore, the method was successfully extended to a diverse array of carboxylic acids in the presence of di--butyl peroxide (DTBP), significantly broadening its applicability.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.4c03933DOI Listing

Publication Analysis

Top Keywords

enantioselective propargylic
8
propargylic csp-h
8
csp-h acyloxylation
8
photoexcited copper
8
copper catalysis
8
acyloxylation enabled
4
enabled photoexcited
4
catalysis direct
4
direct c-h
4
c-h bond
4

Similar Publications

Catalytic Asymmetric Oxidative Coupling between C(sp)-H Bonds and Carboxylic Acids.

J Am Chem Soc

December 2024

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.

The direct enantioselective functionalization of C(sp)-H bonds in organic molecules could fundamentally transform the synthesis of chiral molecules. In particular, the enantioselective oxidation of these bonds would dramatically change the production methods of chiral alcohols and esters, which are prevalent in natural products, pharmaceuticals, and fine chemicals. Remarkable advances have been made in the enantioselective construction of carbon-carbon and carbon-nitrogen bonds through the C(sp)-H bond functionalization.

View Article and Find Full Text PDF

Herein, we report an enantioselective Pd/Cu-catalyzed sequential Heck/Sonogashira coupling reaction of electron-rich enamides with terminal alkynes as substrates. This transformation proceeds smoothly to afford 3-propargyl isoindolinone derivatives bearing quaternary stereogenic centers in moderate to good yields (43-77% yield) and good to excellent enantioselectivity (up to 93% ee). Functional groups such as halogen atoms (F, Cl, and Br), thienyl, and silyl moieties are tolerated well.

View Article and Find Full Text PDF

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 PDF

Copper(I)-Catalyzed Enantioselective α-Alkylation of 2-Acylimidazoles.

J Am Chem Soc

December 2024

Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Catalytic asymmetric α-alkylation of simple carboxylic acid derivatives is a challenging issue due to the difficulties in achieving high catalytic efficiency and controlling the enantioselectivity. Herein, by using a copper(I)-()-DTBM-SEGPHOS complex as a catalyst and 2-acylimidazoles as pronucleophiles, a general method for the catalytic asymmetric α-alkylation of simple carboxylic acid derivatives is accomplished. Various alkyl electrophiles, including allyl bromides, benzyl bromides, propargyl bromide, and unactivated alkyl sulfonates, serve as efficient alkylation reagents.

View Article and Find Full Text PDF

Enantioselective regiospecific addition of propargyltrichlorosilane to aldehydes catalyzed by biisoquinoline ,-dioxide.

Beilstein J Org Chem

November 2024

Department of Chemistry and Chemical Engineering, Florida Institute of Technology, 150 West University Boulevard, Melbourne, Florida 32901-6975, USA.

Article Synopsis
  • - The study successfully created a pure form of propargyltrichlorosilane and developed a new method for its reaction with aldehydes using asymmetric catalytic techniques.
  • - Researchers found that the relationship between the catalyst's structure and its effectiveness in producing specific enantiomers differs from similar reactions involving allylation.
  • - A total of eleven α-allenic alcohols were synthesized from the reaction, yielding different amounts and enantiomeric ratios, and potential reaction mechanisms were explored using computational methods.
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!