α-Halo thioesters undergo soft enolization and syn-selective direct aldol addition to aldehydes in the presence of MgBr(2)·OEt(2) and i-Pr(2)NEt to produce α-halo-β-hydroxy thioesters.
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http://dx.doi.org/10.1039/c0cc02345k | DOI Listing |
JACS Au
November 2024
School of Chemistry, Sun Yat-sen University, Guangzhou 510006, P.R. China.
ChemSusChem
August 2024
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China.
Electrochemical reduction of CO into valuable multicarbon (C) liquids is crucial for reducing CO emissions and advancing clean energy, yet mastering efficiency and selectivity in this process remains a tough challenge. Herein, we employ a surface-modification strategy using electrochemically active polymeric 1,4,5,8-naphthalenete-tracarboxylic dianhydride (PNTCDA)-modified copper nanosheets (PM-Cu) to rearrange reactive species in the electric double layer, where the PNTCDA triggers a distinctive enolization that anchor potassium ions (K) onto the cathode surface under reduction condition. Electrochemical analysis and computational simulations revealed that this approach fine-tunes K distribution in the double layer, making the dehydration of hydrated K more efficient and reducing active water molecules at the interface, thus inhibiting the hydrogen evolution reaction while concurrently promoting CO reduction via enhanced C-C coupling.
View Article and Find Full Text PDFOrg Lett
July 2023
Department of Chemistry, York University, 4700 Keele Street, Toronto, ON M3J 1P3, Canada!
We report a mild method for the synthesis of scaffolds bearing 4-pyridine and 4-piperidine moieties joined by a substituted methylene group. The method exploits the latent nucleophilicity of 4-alkylpyridines and the inherent electrophilicity of pyridines. 4-Alkylpyridines are transformed into nucleophilic alkylidene dihydropyridines (ADHPs) through a soft enolization approach using triethyl amine and chloroformate reagents.
View Article and Find Full Text PDFJ Am Chem Soc
November 2022
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
The total syntheses of aflastatin A and its C3-C48 degradation fragment (, R = H) have been accomplished. The syntheses feature several complex diastereoselective fragment couplings, including a Felkin-selective trityl-catalyzed Mukaiyama aldol reaction, a chelate-controlled aldol reaction involving soft enolization with magnesium, and an anti-Felkin-selective boron-mediated oxygenated aldol reaction. Careful comparison of the spectroscopic data for the synthetic C3-C48 degradation fragment to that reported by the isolation group revealed a structural misassignment in the lactol region of the naturally derived degradation product.
View Article and Find Full Text PDFACS Omega
September 2022
Cluster for Science, Technology and Innovation Hub, Nakamura Laboratory, RIKEN, Wako, Saitama 351-0198, Japan.
The rate of the Rubisco carboxylase reaction is evaluated by statistical mechanics and hybrid density functional theory (DFT). The Rubisco molecular model given by Kannappan et al. was modified and used in the present calculation.
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