Herein, we present a base-mediated nucleophilic substitution reaction of α-trifluoromethylstyrenes with simple silyl enol ethers, enabling the efficient synthesis of carbonyl-substituted -difluoroalkenes. The merit of this protocol is exhibited by its mild reaction conditions, broad substrate scope, and scalable preparation. Notably, this method demonstrates its applicability for late-stage functionalization of structurally complex molecules. Moreover, we illustrate that the resulting products can serve as valuable precursors for the synthesis of diverse medicinally relevant compounds.
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http://dx.doi.org/10.1021/acs.orglett.3c02845 | DOI Listing |
RSC Adv
January 2025
Department of Chemistry, Università degli Studi di Milano Via Camillo Golgi, 19 20133 Milano Italy https://www.fasanolab.com.
Pyridines can be deuterated at the remote sites by treatment with KOBu in DMSO- , although without discrimination between the - and -position. Herein, base-catalyzed deuterations have been studied, computationally and experimentally, using a series of pyridyl phosphonium salts with a temporary electron-withdrawing group to block the -position while increasing the acidity in the other positions.
View Article and Find Full Text PDFMolecules
December 2024
School of Material Science and Engineering, Dalian Jiaotong University, Dalian 116028, China.
An effective method for the construction of functionalized indolizines has been developed in which β,β-difluoro peroxides act as novel C2-building blocks to implement [3+2] annulation with pyridinium ylides under base-mediated conditions. With this protocol, a broad range of multisubstituted indolizines were prepared in moderate to good yields under mild conditions, and many useful functional groups were tolerated.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
School of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China.
Using CO as the C1 source for N-formylation of amine is a crucial energy-storage pathway to address the greenhouse effect while generating high-value-added chemicals but is limited by the activation of inert molecules. Herein, a dual active site catalyst with high CO activation and dihydrogen dissociation capacity was fabricated by incorporating a Schiff base and Au nanoparticles (NPs) on silicon dioxide (SiO). The modification of the Schiff base not only provides an alkaline environment for CO absorption but also stabilizes Au NPs in a small and highly dispersed state, which regulates the electronic density of the metal for excellent H cleavage.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Guwahati, North Guwahati, Assam 781039, India.
Herein, an organocatalytic asymmetric desymmetrizing [4+2] cycloaddition/base-mediated oxidative aromatization reaction sequence has been developed between spirophthalide 2,5-cyclohexadienones and β-methyl cinnamaldehydes. The reaction proceeds through chiral dienamine intermediate formation, and the densely functionalized spirocyclic isobenzofuranone-embedded chiral arenes were formed in high yields with excellent enantioselectivities. A 2-fold desymmetrization reaction was also performed, and the products were obtained in high enantioselectivities.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
Anhui Academy of Science and Technology, HeFei 230088, China.
The expeditious construction of tetrasubstituted furans Cu/base-promoted cascade reactions of terminal alkynes with 1,2-diketones is described. This reaction proceeds smoothly, involving the formation of multiple chemical bonds tolerating a wide range of functional groups. The mechanism underlying these transformations has been thoroughly investigated, suggesting that 1,3-diyne serves as a key intermediate generated through oxidative coupling facilitated by the Cu catalyst.
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