98%
921
2 minutes
20
A photoinduced copper-catalyzed enantioconvergent remote alkynylation of -hydroxyphthalimide esters with terminal alkynes via 1,4-heteroaryl migration has been developed. A broad scope of heteroaryl-tethered chiral alkynes has been synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species plays a dual role as both the photoredox and cross-coupling catalyst. This methodology provides a new platform for enantioconvergent remote alkynylations.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.3c03158 | DOI Listing |
J Am Chem Soc
August 2025
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
The use of hydrazones as carbanion equivalents for carbon-carbon bond formation reactions has emerged as a versatile tool for organic synthesis. However, the enantioselective formation of carbon-carbon bonds with hydrazones has been underdeveloped. We have developed a Ru-catalyzed enantioconvergent hydrobenzylation of racemic allylic alcohols using aryl hydrazones as latent alkyl nucleophiles.
View Article and Find Full Text PDFJACS Au
November 2024
Department of Organic Chemistry, Indian Institute of Science, Bangalore560012, India.
Compared to the widely explored enol silanes, the applicability of their extended variants especially as bisvinylogous nucleophiles in enantioselective catalysis has been sparse. Herein, we describe the first enantioselective vinylogous and bisvinylogous allenylic substitution using silyl dienol and trienol ethers, respectively, as a nucleophile. With racemic allenylic alcohols as the electrophile, these enantioconvergent reactions are cooperatively catalyzed by an Ir(I)/(phosphoramidite,olefin) complex and Lewis acidic La(OTf) and display remarkable regio- and diastereoselectivity in most cases.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.
Asymmetric catalytic versions of electricity-driven processes hold immense potential for the sustainable preparation of chiral compounds. However, the involvement of anodic oxidative cross-dehydrogenative coupling events between two distinct nucleophiles makes it challenging for a chiral catalyst to regulate the stereochemistry of the products. Our current electrocatalytic strategy for enantioconvergent cross-dehydrogenative α- and γ-nitroalkylation via radical-based pathways produces an array of enantioenriched nitroesters without supplementary stoichiometric oxidants.
View Article and Find Full Text PDFOrg Lett
October 2023
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing, Jiangsu 210095, People's Republic of China.
A photoinduced copper-catalyzed enantioconvergent remote alkynylation of -hydroxyphthalimide esters with terminal alkynes via 1,4-heteroaryl migration has been developed. A broad scope of heteroaryl-tethered chiral alkynes has been synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species plays a dual role as both the photoredox and cross-coupling catalyst.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2020
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
An organocatalytic enantioconvergent synthesis of chiral tetrasubstituted allenes is disclosed. With suitable chiral phosphoric acid catalysts, a range of racemic indole-substituted propargylic alcohols reacted with nucleophiles to provide efficient access to a series of enantioenriched allenes with high enantioselectivities. Control experiments suggested a mechanism involving remotely controlled asymmetric 1,8-addition of the in situ generated indole imine methide via a bifunctional transition state.
View Article and Find Full Text PDF