Chiral propargylic cyanides are often used as small-molecule feedstocks for the introduction of chiral centers into various valuable products and complex molecules. Here, we have developed a highly atom-economical strategy for the chiral copper complex-catalyzed synthesis of chiral propargylic cyanides. Propargylic radicals can be smoothly obtained by direct decarboxylation of the propargylic carboxylic acids without preactivation. The reactions show excellent selectivity and functional group compatibility. Gram-scale reaction and several conversion reactions from chiral propargylic cyanide have demonstrated the synthetic value of this strategy.
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http://dx.doi.org/10.1021/acs.orglett.3c01637 | DOI Listing |
J Am Chem Soc
January 2025
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 PDFChemistry
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 PDFAcc Chem Res
December 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Org Lett
November 2024
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.
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.
View Article and Find Full Text PDFBeilstein J Org Chem
October 2024
State Key Laboratory of Structural Chemistry, and Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.
The catalytic (asymmetric) allylation and propargylation have been established as powerful strategies allowing access to enantioenriched α-chiral alkenes and alkynes. In this context, combining allylic and propargylic substitutions offers new opportunities to expand the scope of transition metal-catalyzed substitution reactions. Since its discovery in 2022, copper-catalyzed yne-allylic substitution has undergone rapid development and significant progress has been made using the key copper vinyl allenylidene intermediates.
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