A palladium-catalyzed intramolecular isoindolinone-forming aminooxygenation of alkenes with 1 atm of oxygen as oxidant is reported. A variety of functionalized alkenes and carboxylic acids can be used, and high yields were observed. Preliminary mechanistic studies revealed that the aminooxygenation products were formed through the oxidation of a C-Pd(II) species using a strong oxidant, peroxide, which is generated in situ from a Pd(OAc)2/bpy/O2/HOAc catalytic system.
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http://dx.doi.org/10.1021/acs.orglett.5b02703 | DOI Listing |
Despite the maturity of alkene 1,2-difunctionalization reactions involving C-N bond formation, a key limitation across aminofunctionalization methods is incompatibility with substrates bearing medicinally relevant N-heterocycles. Using a cooperative ligand-substrate catalyst activation strategy, we have developed an aerobic, copper-catalyzed alkene aminooxygenation method that exhibits broad tolerance for β,γ-unsaturated carbamates bearing aromatic azaheterocycle substitution. The synthetic potential of this methodology was demonstrated by engaging a densely-functionalized vonoprazan analogue and elaborating an amino oxygenated product to synthesize a heteroarylated analogue precursor of the FDA-approved antibiotic chloramphenicol.
View Article and Find Full Text PDFJ Am Chem Soc
June 2023
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260, United States.
Alkene aminooxygenation and dioxygenation reactions that result in carbonyl products are uncommon, and protocols that control absolute stereochemistry are rare. We report herein catalytic enantioselective alkene aminooxygenation and dioxygenation that directly provide enantioenriched 2-formyl saturated heterocycles under aerobic conditions. Cyclization of substituted 4-pentenylsulfonamides, catalyzed by readily available chiral copper complexes and employing molecular oxygen as both oxygen source and stoichiometric oxidant, directly provides chiral 2-formyl pyrrolidines efficiently.
View Article and Find Full Text PDFJ Am Chem Soc
October 2022
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described. The procedure employs a trisaminocyclopropenium (TAC) ion catalyst with visible light irradiation under a controlled electrochemical potential to convert aryl olefins to the corresponding oxazolines with high chemo- and diastereoselectivity. With the judicious choice between two inexpensive and abundant reagents, namely water and urethane, either 2-amino-1-ol or 1-amino-2-ol derivatives could be prepared from the same substrate.
View Article and Find Full Text PDFOrg Lett
October 2022
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China.
Angew Chem Int Ed Engl
September 2021
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P. R. China.
A tunable photocatalytic method is reported for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes using readily accessible ketoxime carbonates as the diverse functionalization reagents. Mechanistic studies reveal that this reaction is initiated through an energy-transfer-promoted N-O bond homolysis of ketoxime carbonates leading to alkoxylcarbonyloxyl and iminyl radicals under visible-light photocatalysis, followed by the addition of alkoxylcarbonyloxyl radical to alkenes. By taking advantage of the different stability of the iminyl radicals, the generated carbon radical either abstracts a hydrogen atom from the media to form the anti-Markovnikov hydrooxygenation product, or it is trapped by the persistent iminyl radical to furnish the aminooxygenation product.
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