Schmidt reaction of .alpha.-aralkyl substituted carboxylic acids

Palmere, Raymond M.; Conley, Robert T.

doi:10.1021/jo00833a049

Cited by 13 publications

(4 citation statements)

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“…A-769662, a reversible activator of AMPK, was from Tocris Bioscience (Bristol, UK). 3-Aminopyridine adenine dinucleotide (AAD), a NAD ϩ analog that increases the cellular concentration of NAD ϩ by inhibiting dehydrogenases (27), was synthesized from nicotinic acid adenine dinucleotide and sodium azide as described (28). Recombinant histone H3.3, BstXI, and PshAI were from New England BioLabs (Ipswich, MA).…”

Section: Methodsmentioning

confidence: 99%

Sirtuin 1 Is a Key Regulator of the Interleukin-12 p70/Interleukin-23 Balance in Human Dendritic Cells

Álvarez

Rodríguez

Municio

et al. 2012

Journal of Biological Chemistry

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Stimulation of human dendritic cells with the fungal surrogate zymosan produces IL-23 and a low amount of IL-12 p70. Trans-repression of il12a transcription, which encodes IL-12 p35 chain, by proteins of the Notch family and lysine deacetylation reactions have been reported as the underlying mechanisms, but a number of questions remain to be addressed. Zymosan produced the location of sirtuin 1 (SIRT1) to the nucleus, enhanced its association with the il12a promoter, increased the nuclear concentration of the SIRT1 co-substrate NAD(+), and decreased chromatin accessibility in the nucleosome-1 of il12a, which contains a κB-site. The involvement of deacetylation reactions in the inhibition of il12a transcription was supported by the absence of Ac-Lys-14-histone H3 in dendritic cells treated with zymosan upon coimmunoprecipitation of transducin-like enhancer of split. In contrast, we did not obtain evidence of a possible effect of SIRT1 through the deacetylation of c-Rel, the central element of the NF-κB family involved in il12a regulation. These data indicate that an enhancement of SIRT1 activity in response to phagocytic stimuli may reduce the accessibility of c-Rel to the il12a promoter and its transcriptional activation, thus regulating the IL-12 p70/IL-23 balance and modulating the ongoing immune response.

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Section: Methodsmentioning

confidence: 99%

Sirtuin 1 Is a Key Regulator of the Interleukin-12 p70/Interleukin-23 Balance in Human Dendritic Cells

Álvarez

Rodríguez

Municio

et al. 2012

Journal of Biological Chemistry

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“…How ever, acids containing alkyl or aryl substituents in the a position undergo secondary reactions. For example, aadimethylpropionic ("trimethylacetic") acid 108 forms a mixture of several products: (CH 3 ) 3 CCOOH • o I' CH 3 NH 2 + CH,CCH 3 + NH 3 + CO + 0O 2 A similar pattern is observed with 2-methyl-2-phenylhexanoic acid 91 ' 109 . These departures from the "normal" reaction are due to decarboxylation of the initial acid to the corresponding carbocation and its subsequent reactions: …”

Section: Applications Of Reactionmentioning

confidence: 75%

Schmidt Reaction with Aldehydes and Carboxylic Acids

Koldobskii¹,

Островский²,

Gidaspov³

1978

Russ. Chem. Rev.

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“…Schmidt rearrangement (pathway a) with loss of N 2 gives the isocyanate, which undergoes hydrolysis with decarboxylation to benzylamine. Alternatively, however (pathway b), intramolecular electrophilic aromatic substitution leads to 3; deprotonation produces protonated oxoindole (4). Further reaction with azide leads to o-aminobenzylamine (5).…”

Section: Resultsmentioning

confidence: 99%

“…The product was purified on a silica gel column, eluting with 3 : 1 hexane-ethyl acetate to give powdery biphenyl 2-amino-4Ј-tert-butyl carbamate (the free base of 19, R = BocNH; 285 mg, 22%); mp 140-141 ЊC; 1 H NMR (CDCl 3 ) δ 1.55 (s, 9 H), 3.75 (br, 2 H), 6.5 (br, 1 H), 6.8 (m, 2 H), 7.1 (m, 2 H), 7.4 (q, 4 H); 13 C NMR CDCl 3 δ 28. 4 In a second experiment, the reaction time was extended to 15 h with heating at reflux. The product from the aqueous layer was the same as at the 1.5 h reflux experiment, but the crude product after evaporation of the organic layer was different as analyzed by HPLC on a C18 column, eluting with 0.06% TFA in acetonitrile and water (50 : 50) at 254 nm and a flow rate of 1 mL min Ϫ1 .…”

Section: Reaction Of 4ј-trifluoromethylbiphenyl-2-carboxylic Acid (12...mentioning

confidence: 99%

Anomalous Schmidt reaction products of phenylacetic acid and derivatives

Woodroofe

Zhong

et al. 2000

J. Chem. Soc., Perkin Trans. 2

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Treatment of carboxylic acids with sodium azide in sulfuric acid normally results in decarboxylation with conversion of the carboxylic acid to an amine (the Schmidt reaction). However, many side reactions have been reported to occur, particularly in the case of α-aryl carboxylic acids, such as sulfonation, direct amination of the phenyl ring, cyclization to a lactam, and elimination of side chains to give aniline. In this study, the reactions of a variety of analogues of phenylacetic acid under given reaction conditions are examined to determine which characteristics are important in the competing side reactions. Some reactions were carried out with TEMPO free radical as a radical scavenger to investigate whether direct amination proceeds by a radical intermediate. Phenylacetic acid is shown to give an orthoaminated diamine product instead of the para-aminated one expected from direct amination. A mechanism for this side reaction, involving cyclization to a lactam intermediate followed by further cleavage, is proposed; an analogue of the hypothetical intermediate has been isolated for biphenylacetic acids.

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Schmidt reaction of .alpha.-aralkyl substituted carboxylic acids

Cited by 13 publications

References 1 publication

Sirtuin 1 Is a Key Regulator of the Interleukin-12 p70/Interleukin-23 Balance in Human Dendritic Cells

Sirtuin 1 Is a Key Regulator of the Interleukin-12 p70/Interleukin-23 Balance in Human Dendritic Cells

Schmidt Reaction with Aldehydes and Carboxylic Acids

Anomalous Schmidt reaction products of phenylacetic acid and derivatives

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