Ethyl 5,5-diarylpenta-2,3,4-trienoates were synthesized and utilized in the phosphine-mediated [3+2] cycloaddition reactions with arylmethylidenemalononitriles and N-tosylimines in the presence of tributylphosphine. These reactions provide an easy access to a variety of novel polysubstituted cyclopentenes or pyrrolidines in good to excellent yields under mild conditions.
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http://dx.doi.org/10.1021/jo802489t | DOI Listing |
ACS Sens
January 2025
College of Chemistry and Chemical Engineering, Xinyang Key Laboratory of Functional Nanomaterials for Bioanalysis, Xinyang Normal University, Xinyang 464000, China.
To advance the biological understanding of heat shock protein (HSP) in different types of cancers, it is crucial to achieve its accurate determination. Herein, a dual-mode self-powered photoelectrochemical (PEC) and colorimetric platform was proposed by integrating enzymatic catalysis and a chemical redox cycling amplification strategy. In this system, ascorbic acid (AA), as the signal reporter for PEC and colorimetric assay, can be regenerated during the tris(2-carboxyethyl) phosphine-mediated chemical redox cycling process.
View Article and Find Full Text PDFOrg Lett
January 2025
Departamento de Química Orgánica, Facultad de Química, Regional Campus of International Excellence "Campus Mare Nostrum", Universidad de Murcia, E-30100Murcia, Spain.
Intramolecular reactions between isocyano and iminophosphorane functions yield species containing an embedded 1,3,2-diazaphosphetidine ring, as result of the [2 + 2] cycloaddition of the primary reactive product, the cyclic carbodiimide, with a second unit of reactant. DFT studies reveal a first rate-determining step entailing a [2 + 1] cycloaddition involving the isocyanide carbon atom and the P═N double bond, with the further intervention of a dipolar precursor of the intermediate carbodiimide. The 1,3,2-diazaphosphetidine ring of the final products is shown to be hydrolytically and thermally labile.
View Article and Find Full Text PDFOrg Lett
October 2024
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, United States.
We report a phosphine-mediated cyclodehydration procedure for the facile synthesis of -aryl/alkyl-substituted hydrazonyl sultones, a class of bioorthogonal reagents, from the readily prepared vicinal sulfo-acyl hydrazides in moderate to good yields. The aqueous stability and bioorthogonal reactivity of these hydrazonyl sultones toward bicyclo[6.1.
View Article and Find Full Text PDFOrg Lett
September 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Stable and easy-to-handle sodium salts of sulfonyl oximes were first identified to proceed via visible-light-driven phophine-mediated successive deoxygenation to realize the -Markovnikov hydrothiolation of alkenes, which could serve as an odorless sulfur source. Mechanistic studies revealed that the key thiyl radical intermediate could be generated from the sulfonyl oxime anion via a phosphine-mediated fragmentation and a sequential deoxygenation process. Notably, a wide range of alkenes, including acrylamides, acrylates, vinyl ketones, vinyl sulfones, and acrylonitriles, are competent substrates for this protocol, which is highly beneficial for the construction of structurally diversified organosulfur compounds.
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September 2024
College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, P. R. China.
Herein, we report an unprecedented P(NMe)-mediated reductive insertion of 1,2-dicarbonyl compounds including α-keto esters and isatins into phthalic anhydride-derived alkenes and phthalic anhydrides, which furnishes the corresponding isochroman-1-ones and isochroman-1,4-diones, respectively, in moderate to excellent yields with high chemo- and regioselectivity. Furthermore, the asymmetric version of the ring expansion reaction could be realized by using a chiral auxiliary strategy. Mechanistically, the nucleophilic attack of the Kukhtin-Ramirez adduct, generated from P(NMe) and 1,2-dicarbonyl compound, to the anhydride derivative, followed by a cascade ring-opening and ring-closure process, affords the ring expansion product.
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