Stoichiometric cyclomanganation of aromatic ketones and further reactions of the thus-formed manganacycles with isocyanates were first reported by Kaesz and Liebeskind in 1975 and 1990, respectively. The buildup of a closed manganese catalytic cycle for the reaction of ketones and isocyanates remains an unsolved problem. Herein, an unprecedented trio of MeZn/AlCl/AgOTf is developed to build up manganese catalysis, which enables the [3 + 2] cyclization of ketones with isocyanates via inert C-H activation to access 3-alkylidene phthalimidines in a straightforward manner unachieved by other transition metal catalyses.
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http://dx.doi.org/10.1021/acs.orglett.1c00857 | DOI Listing |
J Org Chem
November 2024
Department of Chemistry and Biochemistry, Baylor University, One Bear Place #97348, Waco, Texas 76798-7348, United States.
Chlorosulfonyl isocyanate (CSI) is a complex reagent capable of facilitating numerous synthetic transformations, including lactam/lactone formation, sulfonylation, Friedel-Crafts-type acylations, and cycloadditions. Annulation reactions to form nitrogen-, oxygen-, and sulfur-bearing heterocycles have been observed with CSI; however, the application of CSI toward the generation of fused cyclic ketone ring systems has not been previously reported. A serendipitous discovery of the pertinence of CSI occurred during a structure-activity relationship campaign around our established lead benzosuberene-based molecule that functions as a potent inhibitor of tubulin polymerization.
View Article and Find Full Text PDFJ Agric Food Chem
May 2024
Department of Food Science and Nutrition, University of Minnesota, 1334 Eckles Avenue, St. Paul, Minnesota 55108, United States.
A C-based method was developed to study the rate and extent of covalent bond formation between β-lactoglobulin and three model flavor compounds: a ketone (2-undecanone UDO), an aldehyde (decanal DAL), an isothiocyanate (2-phenylethyl isothiocyanate PEITC), and an unreactive "methods blank" (decane DEC). Aqueous protein solutions with one of the C-labeled model flavor compounds were placed in water baths at 25, 45, and 65 °C for 4 weeks measuring the amount of flavor: protein reaction at 1, 3, 7, 14, 21, and 28 days. UDO showed lowest reactivity (max of 0.
View Article and Find Full Text PDFInt J Mol Sci
March 2024
Grupo de Investigación de Compuestos Heterocíclicos, Departamento de Química, Universidad del Valle, Cali 760042, Colombia.
This study presents the synthesis of four series of novel hybrid chalcones ()- and ()- and six series of 1,3,5-triazine-based pyrimido[4,5-][1,4]diazepines (-)- and the evaluation of their anticancer, antibacterial, antifungal, and cytotoxic properties. Chalcones ,, ,, ,-, - and the pyrimido[4,5-][1,4]diazepines ,, , ,,-, ,,- exhibited outstanding anticancer activity against a panel of 60 cancer cell lines with GI values between 0.01 and 100 μM and LC values in the range of 4.
View Article and Find Full Text PDFEnviron Sci Process Impacts
April 2024
International Isocyanate Institute, Inc., Mountain Lakes, NJ, USA.
Chemistry
January 2024
Chemistry and Biochemistry Program, Schmid College of Science and Technology, Chapman University, 450 North Center Street, Orange, CA 92866, USA.
We report hydroboration of carbodiimide and isocyanate substrates catalyzed by a cyclic carbodiphosphorane catalyst. The cyclic carbodiphosphorane outperformed the other Lewis basic carbon species tested, including other zerovalent carbon compounds, phosphorus ylides, an N-heterocyclic carbene, and an N-heterocyclic olefin. Hydroborations of seven carbodiimides and nine isocyanates were performed at room temperature to form N-boryl formamidine and N-boryl formamide products.
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