Intermolecular reaction of an aryl nitrene

Odum, Robert A.; Aaronson, Alan M.

doi:10.1021/ja01048a066

Cited by 39 publications

(10 citation statements)

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“…Further, incubation of 3 with a 25-fold excess of ro-butylamine did not yield any addition products (data not presented). This result is consistent with previous reports which indicate that, in general, arylnitrenes having strongly electronegative ring substituents are less likely to form azepines than are more electron-rich compounds (22,23,25).…”

Section: Discussionsupporting

confidence: 93%

Arylamine-Nucleoside Adduct Formation: Evidence for Arylnitrene Involvement in the Reactions of an N-Acetoxyarylamine

Boteju

Hanna²

1994

Chem. Res. Toxicol.

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N-Acetoxyarylamines are reactive metabolites that are produced from N-arylhydroxamic acids by N-arylhydroxamic acid N,O-acyltransferase and by the acetyl coenzyme A-dependent O-acetylation of N-arylhydroxylamines. Solvolytic decomposition of 7-acetyl-2-(N-acetoxyamino)fluorene (3) afforded 7-acetyl-2-aminofluorene (4) and 7,7'-diacetyl-2,2'-azofluorene (5). Solvolysis of 3 in the presence of 2'-deoxyguanosine resulted in formation of N-(deoxyguanosin-8-yl)-7-acetyl-2-aminofluorene (2), along with smaller yields of 4 and 5 than were obtained in the absence of 2'-deoxyguanosine. The inclusion of nitrene trapping agents, such as piperylene, triethyl phosphite, 1-chloro-4-nitrosobenzene, and oxygen, in the reaction medium with 3 and 2'-deoxyguanosine caused a reduction in the yields of 2, 4, and 5. Additionally, products that would be expected to be formed through reaction with an arylnitrene intermediate were obtained when triethyl phosphite, 1-chloro-4-nitrosobenzene, and oxygen were included in the incubations with 3 and 2'-deoxyguanosine. The results support the proposal that a nitrene intermediate is involved in the formation of 2, 4, and 5 from 3.

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Section: Discussionsupporting

confidence: 93%

Arylamine-Nucleoside Adduct Formation: Evidence for Arylnitrene Involvement in the Reactions of an N-Acetoxyarylamine

Boteju

Hanna²

1994

Chem. Res. Toxicol.

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“…1 Cambridge NeuroScience, Inc. nation (18). Photolysis of m-or p-chlorophenyl azides in dimethylamine has been shown to give ring-expansion products (19,20). Herein we report the synthesis and photochemical properties of the tetrasubstituted functionalized CPA methyl 4-azido-2,3,5,6-tetrachlorobenzoate (3), and the ortho,ortho'-disubstituted CPA methyl 4-azido-3,5-dichlorobenzoate (4).…”

Section: Introductionmentioning

confidence: 99%

Chlorinated phenyl azides as photolabeling reagents. Synthesis of an ortho,ortho'-dichlorinated arylazido PCP receptor ligand

Cai¹,

Glenn²,

Gee³

et al. 1993

Bioconjugate Chem.

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The enhanced photolabeling properties of chlorinated phenyl azides are demonstrated by the synthesis and photolysis of methyl 4-azido-2,3,5,6-tetrachlorobenzoate (3) and methyl 4-azido-3,5-dichlorobenzoate (4). Photolysis of azide 3 in 1 M diethylamine/cyclohexane as the trapping medium gave 34% NH-insertion product. Similar photolysis of azide 4 gave 35% NH insertion product. These results demonstrate that chlorinated phenyl azides are significantly better at undergoing NH insertion than nonhalogenated analogs and suggest that improvement of existing aryl azide-based photolabels might be achieved by introduction of chlorine atoms on either side of the azide group. As an application, 3-azido-2,4-dichloro-10,5-(iminomethano)-10,11-dihydro-5H- dibenzo[a,d]cycloheptene (19), an analog of the potent PCP receptor ligand IDDC (14), was synthesized and its affinity for the PCP receptor was determined to be 6.3 +/- 0.7 microM (IC50 against [3H]MK801).

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“…A number of 2-substituted 3H-azepines were known when our investigation was initiated. 27,28,33 We were particularly interested in the photochemistry of 2-dimethylamino-3H-azepine, 28 2-amino-3H-azepine 27 and 2-ethoxy-3H-azepine. Our studies showed that these compounds underwent selective photoelectrocyclization to 3-substituted 2-azabicyclo[3.2.0]hepta-2,6-dienes.…”

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confidence: 99%