1,1-Disubstituted aryl cyclopropyl nitriles are useful moieties in biologically active compounds and provide access to a range of cyclopropyl derivatives. Herein, we describe the development of a palladium-catalyzed α-arylation of cyclopropyl, cyclobutyl, and cyclopentyl nitriles that affords these functional groups in one step from a variety of aryl bromides in good to excellent yields. Furthermore, we demonstrate the transformation of aryl cyclopropyl nitriles into aryl trifluoromethyl cyclopropanes.
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http://dx.doi.org/10.1021/ol5030426 | DOI Listing |
Org Biomol Chem
August 2022
SANKEN, Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047, Japan.
Angew Chem Int Ed Engl
August 2022
Department of Chemistry and Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen, 518055, China.
The first rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)-DTBM-Yanphos, can convert a series of readily available cyclopropyl-functionalized trisubstituted alkenes into high-value chiral cyclopropyl-functionalized aldehydes with high selectivities (81-98 % ee). Gram-scale reactions (TON up to 1500) and follow-up transformations to the corresponding alcohol, acid, esters and nitrile are also presented.
View Article and Find Full Text PDFJ Phys Chem A
July 2021
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706-1322, United States.
The gas-phase rotational spectrum of (cyanomethylene)cyclopropane, (CH)C═CHCN, generated by a Wittig reaction between the hemiketal of cyclopropanone and (cyanomethylene)triphenylphosphorane, is presented for the first time. This small, highly polar nitrile is a cyclopropyl-containing structural isomer of pyridine. The rotational spectra of the ground state and two vibrationally excited states were observed, analyzed, and least-squares fit from 130 to 360 GHz.
View Article and Find Full Text PDFSci Total Environ
December 2020
School of Biomedical and Pharmaceutical Sciences, Guangdong University of Technology, Guangzhou 510006, People's Republic of China. Electronic address:
Photochemical methods attracted much research interests for their high-efficiency and low secondary pollution. Decomposition of synthetic pyrethroids, the fourth major group of insecticides in use worldwide, was also of great significance due to their possible environmental risks. The photodegradation of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids in methanol/acetone = 9/1 (by volume) by a 400 W mercury lamp was examined.
View Article and Find Full Text PDFBiochem Pharmacol
June 2019
Neuprozyme Therapeutics A/S, 2970 Hörsholm, Denmark. Electronic address:
Cathepsin C (CatC) is a dipeptidyl-exopeptidase which activates neutrophil serine protease precursors (elastase, proteinase 3, cathepsin G and NSP4) by removing their N-terminal propeptide in bone marrow cells at the promyelocytic stage of neutrophil differentiation. The resulting active proteases are implicated in chronic inflammatory and autoimmune diseases. Hence, inhibition of CatC represents a therapeutic strategy to suppress excessive protease activities in various neutrophil mediated diseases.
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