Manganese-Catalyzed [3 + 2] Cyclization of Ketones and Isocyanates via Inert C-H Activation.

Org Lett

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Published: May 2021

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.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.1c00857DOI Listing

Publication Analysis

Top Keywords

ketones isocyanates
12
cyclization ketones
8
isocyanates inert
8
inert c-h
8
c-h activation
8
manganese-catalyzed cyclization
4
ketones
4
isocyanates
4
activation stoichiometric
4
stoichiometric cyclomanganation
4

Similar Publications

Application of Chlorosulfonyl Isocyanate (CSI) in the Synthesis of Fused Tetracyclic Ketone Ring Systems.

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 PDF

C-Isotope Use to Quantify Covalent Reactions between Flavor Compounds and β-Lactoglobulin.

J 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 PDF

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 PDF
Article Synopsis
  • The formation of phosgene from bleach powder is disputed due to a lack of a clear carbon source.
  • Other factors not addressed by the authors might have impacted the results, potentially leading to misleading conclusions.
  • The study raises concerns about the accuracy of the findings regarding the chemical reactions involved.
View Article and Find Full Text PDF

Carbodiimide and Isocyanate Hydroboration by a Cyclic Carbodiphosphorane Catalyst.

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.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!