Pivalophenone N–H imine has been found to serve as a prominent substrate for directed C–H alkylation and arylation reactions with alkyl bromides and aryl chlorides, respectively, under cobalt–N-heterocyclic carbene (NHC) catalysis. Unlike the case of the parent pivalophenone imine, the increased steric bulk of the resulting ortho-substituted pivalophenone imines allows them to undergo clean imi...

The metalation reactions between [Pt2(4-MeC6H4)4(μ-SEt2)2] and 2-X,6-FC6H3CH[double bond, length as m-dash]NCH2CH2NMe2 (X = Br, Cl) have been studied. In all cases, seven-membered platinacycles are formed in a process that involves an initial reductive elimination from cyclometallated Pt(IV) intermediate compounds, [PtX(4-CH3C6H4)2(ArCH[double bond, length as m-dash]NCH2CH2NMe2)] (X = Br, Cl), ...

Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary a...

The Kabachnik-Fields (phospha-Mannich) reaction involving the condensation of primary or secondary amines, oxo compounds (aldehydes and ketones) and >P(O)H species, especially dialkyl phosphites, represents a good choice for the synthesis of α-aminophosphonates that are of significant importance due to their biological activity. In general, these three-component reactions may take place via a...

For the class A β-lactamase SHV-1, the kinetic and mechanistic properties of the clinically used inhibitor sulbactam are compared with the sulbactam analog substituted in its 6β position by a CH2OH group (6β-(hydroxymethyl)penicillanic acid). The 6β substitution improves both in vitro and microbiological inhibitory properties of sulbactam. Base hydrolysis of both compounds was studied by Raman ...

Atmospheric brown carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report on a series of laboratory studies of photochemical processing of BrC in the aqueous ...

Kinetics and mechanisms of the imine exchange reactions of O-alkyl and O-aryl oximes with O-alkyland O-aryloxyamines, respectively, were studied by H NMR spectroscopy in aqueous solutions. The reaction between benzaldehyde O-methyloxime and O-ethylhydroxylamine at 60°C is first order in both oxime and the alkoxylamine (the second-order rate constant k2 = 0.86 0.08 l molÿ1 minÿ1 at pD 2.9), the ...

BACKGROUND Heteronucleophiles as well as carbanionic reagents can be used to react with α-amido sulfones, thus giving the opportunity to prepare a large array of amino derivatives. Since, novel 1,3,4-oxadiazole-2-thiol derivatives can serve as potent nucleophiles, we employed 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the nucleophilic source of nitrogen in the reaction with α-amido sulfo...

The photodissociation of the amide bond by UV light and soft x-rays is investigated by x-ray absorption spectroscopy at the C, N, and O 1s edges. Irradiation leaves a clear and universal signature for a wide variety of amides, ranging from oligopeptides to large proteins and synthetic polyamides, such as nylon. As the π∗ peak of the amide bond shrinks, two new π∗ peaks appear at the N 1s edge w...