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Journal of the American Chemical Society Jun 2022A new molecular rearrangement, the -Quasi-Favorskii rearrangement, has been developed for the construction of highly substituted aziridines. Electron-deficient -sulfonyl...
A new molecular rearrangement, the -Quasi-Favorskii rearrangement, has been developed for the construction of highly substituted aziridines. Electron-deficient -sulfonyl oximes react readily with α,α-disubstituted acetophenone-derived enolates to furnish highly substituted aziridines this unprecedented domino process. In-depth computational studies reveal an asynchronous yet concerted nitrenoid-type rearrangement pathway.
Topics: Aziridines; Methylmethacrylates; Molecular Structure; Stereoisomerism
PubMed: 35674783
DOI: 10.1021/jacs.2c03805 -
Journal of Natural Medicines Jan 2024Epoxides, aziridines, and cyclopropanes are found in various medicinal natural products, including polyketides, terpenes, peptides, and alkaloids. Many classes of... (Review)
Review
Epoxides, aziridines, and cyclopropanes are found in various medicinal natural products, including polyketides, terpenes, peptides, and alkaloids. Many classes of biosynthetic enzymes are involved in constructing these ring structures during their biosynthesis. This review summarizes our current knowledge regarding how α-ketoglutarate-dependent nonheme iron enzymes catalyze the formation of epoxides, aziridines, and cyclopropanes in nature, with a focus on enzyme mechanisms.
Topics: Iron; Ketoglutaric Acids; Catalysis; Cyclopropanes; Aziridines; Epoxy Compounds
PubMed: 37980694
DOI: 10.1007/s11418-023-01760-4 -
ChemistryOpen Jun 2024In previous works, we demonstrated that tertiary 3-chloropiperidines are potent chemotherapeutics, alkylating the DNA through the formation of bicyclic aziridinium ions....
In previous works, we demonstrated that tertiary 3-chloropiperidines are potent chemotherapeutics, alkylating the DNA through the formation of bicyclic aziridinium ions. Herein, we report the synthesis of novel secondary 3-chloropiperidine analogues. The synthesis incorporates a new procedure to monochlorinate unsaturated primary amines utilizing N-chlorosuccinimide, while carefully monitoring the temperature to prevent dichlorination. Furthermore, we successfully isolated highly strained bicyclic aziridines by treating the secondary 3-chloropiperidines with a sufficient amount of base. We conclude this work with a DNA cleavage assay as a proof of principle, comparing our previously known substrates to the novel compounds. In this, the secondary 3-chloropiperidine as well as the isolated bicyclic aziridine, proved to be more effective than their tertiary counterpart.
Topics: Piperidines; Antineoplastic Agents, Alkylating; Alkylating Agents; DNA Cleavage; Humans; Aziridines; DNA; Succinimides
PubMed: 38088585
DOI: 10.1002/open.202300181 -
IARC Monographs on the Evaluation of... 1999
Review
Topics: Animals; Aziridines; Carcinogenicity Tests; Carcinogens; Humans; Mutagenicity Tests; Mutagens; Neoplasms, Experimental; Occupational Exposure
PubMed: 10476450
DOI: No ID Found -
Journal of the American Chemical Society Mar 2022We report enantioselective one-carbon ring expansion of aziridines to make azetidines as a new-to-nature activity of engineered "carbene transferase" enzymes. A...
We report enantioselective one-carbon ring expansion of aziridines to make azetidines as a new-to-nature activity of engineered "carbene transferase" enzymes. A laboratory-evolved variant of cytochrome P450, P411-AzetS, not only exerts unparalleled stereocontrol (99:1 er) over a [1,2]-Stevens rearrangement but also overrides the inherent reactivity of aziridinium ylides, cheletropic extrusion of olefins, to perform a [1,2]-Stevens rearrangement. By controlling the fate of the highly reactive aziridinium ylide intermediates, these evolvable biocatalysts promote a transformation which cannot currently be performed using other catalyst classes.
Topics: Azetidines; Aziridines; Carbon; Catalysis; Stereoisomerism
PubMed: 35258294
DOI: 10.1021/jacs.2c00251 -
Organic Letters May 2020Piperazines are prevalent in pharmaceuticals and natural products, but traditional methods do not typically introduce stereochemical complexity into the ring. To expand...
Piperazines are prevalent in pharmaceuticals and natural products, but traditional methods do not typically introduce stereochemical complexity into the ring. To expand access to these scaffolds, we report Rh-catalyzed ring expansions of aziridines and sulfonyl-1,2,3-triazoles to furnish dehydropiperazines with excellent diastereocontrol. Productive ring expansion proceeds via a pseudo-1,4-sigmatropic rearrangement of an aziridinium ylide species. However, the structural features of the carbene precursor are important, as pyridotriazoles undergo competing cheletropic extrusion to furnish ketimines.
Topics: Aziridines; Catalysis; Imines; Molecular Structure; Nitriles; Piperazines; Rhodium; Triazoles
PubMed: 32320259
DOI: 10.1021/acs.orglett.0c01124 -
Vaccine Aug 1990Viral antigens for human and veterinary vaccines are still inactivated with formaldehyde. This is not an ideal inactivant and the problems of formaldehyde inactivation... (Review)
Review
Viral antigens for human and veterinary vaccines are still inactivated with formaldehyde. This is not an ideal inactivant and the problems of formaldehyde inactivation of vaccines are discussed. Vaccines inactivated with aziridines are superior in safety and antigenicity. Aziridines inactivate viruses in a first-order reaction and the inactivation rate and endpoint can be determined. The preparation and application of the aziridine compound binary ethylenimine (BEI) and the necessary conditions for and controls of the inactivation process are described and discussed. A computer program has been written for assistance in the use of BEI for controlled inactivation of viral antigens.
Topics: Animals; Antigens, Viral; Aziridines; Humans; Vaccines, Inactivated
PubMed: 2204242
DOI: 10.1016/0264-410x(90)90083-x -
CA: a Cancer Journal For Clinicians 1964
Topics: Adrenal Cortex Hormones; Antineoplastic Agents; Cyclophosphamide; Dactinomycin; Gonadal Steroid Hormones; Humans; Methotrexate; Neoplasms; Progestins; Quinacrine; Thiotepa; Vinblastine
PubMed: 14129472
DOI: 10.3322/canjclin.14.2.67 -
The British Journal of Cancer.... Jul 1996
Review
Topics: Animals; Antineoplastic Agents; Aziridines; Biotransformation; Indolequinones; Indoles; Mitomycin; NAD(P)H Dehydrogenase (Quinone); Oxidation-Reduction
PubMed: 8763836
DOI: No ID Found -
Bioscience, Biotechnology, and... 2012Synthetic studies of Annonaceous acetogenins isolated from the plant family Annonaceae and marine natural products (miraziridine A, tokaramide A, and callipeltins)... (Review)
Review
Synthetic studies of Annonaceous acetogenins isolated from the plant family Annonaceae and marine natural products (miraziridine A, tokaramide A, and callipeltins) containing unusual amino acids, and recent studies of the structure-activity relationship of cysteine protease inhibitor are described.
Topics: Acetogenins; Animals; Annonaceae; Aziridines; Biological Products; Cysteine Proteinase Inhibitors; Molecular Structure; Oligopeptides; Peptides, Cyclic; Porifera; Structure-Activity Relationship
PubMed: 22785468
DOI: 10.1271/bbb.120176