5553-73-1Relevant academic research and scientific papers
Mutagenicity and DNA damage studies of N-acyloxy-N-alkoxyamides--the role of electrophilic nitrogen.
Banks, Tony M,Bonin, Antonio M,Glover, Stephen A,Prakash, Arungundrum S
, p. 2238 - 2246 (2003)
N-Acyloxy-N-alkoxyamides are anomeric amides that are direct-acting mutagens. They have been shown to damage DNA in the major and the minor grooves in a pH and sequence-selective manner. In acidic media, they damage adenines at N3 in the minor groove but above neutral pH, only guanine is damaged at N7 in the major groove. Both the acyloxy leaving group and the alkoxy group at the amide nitrogen are responsible for their electrophilicity and Salmonella mutagenicities in TA 100 and DNA damage data confirm that the mutagens react with DNA in an intact form, rather than by solvolysis to electrophilic nitrenium ions in the cytosol, or in vitro, prior to reacting with DNA. Hydrophobicity plays a role in both mutagenicity and DNA damage.
Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone
Miyata, Okiko,Koizumi, Tomoko,Asai, Hiroshi,Iba, Ryuichi,Naito, Takeaki
, p. 3893 - 3914 (2007/10/03)
The imino 1,2-Wittig rearrangement of hydroximates provides a novel method for the construction of 2-hydroxyoxime ethers. Upon treatment with LDA, Z-hydroximates smoothly underwent stereoselective rearrangement to give Z-2-hydroxyoxime ethers in good yield, which were converted into amino alcohols. On the other hand, the rearrangement of E-hydroximates gave a mixture of E- and Z-2-hydroxyoxime ethers. This method was successfully applied to a practical synthesis of cytoxazone.
Hindered ester formation by SN2 azidation of N-acetoxy-N-alkoxyamides and N-alkoxy-N-chloroamides-novel application of HERON rearrangements
Glover, Stephen A.,Mo, Guoning
, p. 1728 - 1739 (2007/10/03)
Treatment of N-acetoxy-N-alkoxyamides or N-alkoxy-N-chloroamides with sodium azide in aqueous acetonitrile results in SN2 displacement of chloride and the formation of reactive N-alkoxy-N-azidoamides. The reaction with N-acetoxy-N-benzyloxybenzamide has been studied kinetically (k294 = 2 L mol-1 s-1) and azidation of N-formyloxy-N-methoxyformamide has been modeled computationally at the pBP/DN*//HF/6-31G* level of theory. The anomeric amides N-alkoxy-N-azidoamides decompose intermolecularly and spontaneously to esters and two equivalents of nitrogen. This extremely exothermic process facilitates the formation, in excellent yields, of highly hindered esters.
Reductive cleavage of N-O bonds in hydroxylamines and hydroxamic acid derivatives using samarium diiodide
Keck, Gary E.,Wager, Travis T.,McHardy, Stanton F.
, p. 11755 - 11772 (2007/10/03)
An efficient process for the reductive cleavage of N-O bonds using samarium diiodide is detailed for a variety of structural types to define the scope and limitations of the method. The reduction is shown to be compatible with base sensitive substrates such as trifluoroacetamide derivatives, which cannot be reduced satisfactorily using aluminum amalgam or sodium amalgam. Direct quenching of the reduction mixture with acylating agents is demonstrated to provide high yields of protected amines in a one-pot process from the N-O derivatives.
