An exquisite protocol to the synthesis of erythrina-related structural derivatives was developed, which is composed of a nucleophilic addition of tertiary enamides to ketonic carbonyls and the trapping of acyliminium by an aromatic unit. This protocol afforded a powerful method for the construction of diverse fused -pentacyclic skeletons in high efficiency and excellent diastereoselectivity by just using different acid catalysts.
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http://dx.doi.org/10.1021/acs.orglett.0c03162 | DOI Listing |
Chem Sci
August 2024
School of Chemistry and Chemical Engineering, Shaanxi Normal University Xi'an Shanxi 710062 China
Chiral alpha-amino ketones have found extensive applications as functional molecules. A nickel-catalyzed, enantioselective, and fully intermolecular three-component 1,2-alkylacylation of -acyl enamides has been realized with tertiary alkyl bromides and carboxylic acid-derived electrophiles as the coupling reagents. This reductive coupling strategy is operationally simple, exhibiting broad substrate scope and excellent functional group tolerance using readily available starting materials and allowing rapid access to structurally complex α-amino ketone derivatives in high enantioselectivity.
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August 2024
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, China.
Recent strides in C-H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C-C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies have been proposed for hydroboration of cyclopropanes by activating C-C bonds, conventionally relying on noble and hazardous metal catalysts to control reaction outcomes.
View Article and Find Full Text PDFChemistry
September 2024
Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou, China.
The catalytic direct hydroarylation of alkynamides is a highly efficient approach for accessing functionalized trisubstituted arylalkenes with amide groups. Herein, we report a rhodium-catalyzed pyridylation of alkynamides with pyridylboronic acids, producing a variety of primary, secondary, and tertiary enamides with high yields (up to 94 %). This reaction demonstrates broad tolerance towards various alkyl and aryl functional groups, providing convenient access to a diverse array of alkenylpyridine derivatives.
View Article and Find Full Text PDFChem Commun (Camb)
June 2024
Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi, 755-8611, Japan.
Efficient C-C bond cleavage is recognized as a persistent challenge in the field of synthetic methodology. In this study, we found that tertiary alkyl radicals are smoothly formed from tertiary alkylated dienones (BHT adducts) SET, using PDI as a photocatalyst. Resulting -alkyl radicals could be applied to the -alkylation of enamides.
View Article and Find Full Text PDFOrg Lett
January 2024
College of Materials, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China.
A highly diastereo- and enantioselective phosphinative cyclization of ketone-enamides with secondary diarylphosphines enabled by copper catalysis is reported, providing a range of chiral tertiary cyclohexylphosphines bearing three contiguous stereogenic centers in high yields. This asymmetric phosphination-aldol cyclization protocol can also be extended to desymmetrization of dione-enamides to create four contiguous stereogenic centers in a highly selective manner.
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