Protodediazoniation of Aryldiazonium Fluoroborates by Dimethylformamide [1]

Markgraf, J. Hodge; Chang, Raymond; Cort, John; Durant, Joseph L.; Finkelstein, Manuel; Gross, Andrew; Lavyne, Michael H.; Moore, Cameron M.; Petersen, Raymond C.; Ross, Sidney D.

doi:10.1016/s0040-4020(97)00343-8

Cited by 14 publications

(7 citation statements)

References 53 publications

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“…In order to better understand the mechanism we attempted to use DMF- d 7 as the solvent, which resulted in the formation of 3k in trace amounts and degradation of the starting material, 2k (see Scheme S7). These results suggest that DMF has a crucial role in this cyclization, probably as a terminal HAT species (Scheme b), which is precedented in the literature , (see the Supporting Information for more details). This is in agreement with the absence of product formation when the reaction was performed in MeCN (see Scheme S3).…”

Section: Resultsmentioning

confidence: 99%

“…This is in agreement with the absence of product formation when the reaction was performed in MeCN (see Scheme S3). Comparing bond dissociation energies (BDE) of a primary alkyl radical (BDE [C1–H in propane] = 100 kcal/mol) and DMF (BDE [H–CH 2 N(Me)CHO or Me 2 NC(O)–H] = 89–90 kcal/mol), HAT is feasible. Furthermore, the submission of esters 2l and 2m to the reaction conditions resulted in the isolation of product 3l in slightly lower yield (49%) and detection of product 3m only in traces (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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3-Acetoxyquinuclidine as Catalyst in Electron Donor–Acceptor Complex-Mediated Reactions Triggered by Visible Light

2019

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

3-Acetoxyquinuclidine as Catalyst in Electron Donor–Acceptor Complex-Mediated Reactions Triggered by Visible Light

2019

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“…Finally, we synthesized the deuterated analogue 1c via treatment of 1a with t -butyl nitrite in DMF- d 7 . , Availability of this labeled compound enabled us to undertake isotope-tracking experiments complementary to the solvent-labeling experiments described above. Specifically, the dehydration mechanism proposed to generate radical 6 would result in the loss of deuterium content during the conversion of 1c to 3 when the reaction is carried out in the presence of protic solvents and hydrogen atom sources.…”

Section: Resultsmentioning

confidence: 99%

Isotopic Labeling Experiments That Elucidate the Mechanism of DNA Strand Cleavage by the Hypoxia-Selective Antitumor Agent 1,2,4-Benzotriazine 1,4-Di-N-oxide

Shen

Rajapakse

Gallazzi

et al. 2013

Chem. Res. Toxicol.

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The 1,2,4-benzotriazine 1,4-dioxides are an important class of potential anticancer drugs that selectively kill the low-oxygen (hypoxic) cells found in solid tumors. These compounds undergo intracellular one-electron enzymatic reduction to yield an oxygen-sensitive drug radical intermediate that partitions forward, under hypoxic conditions, to generate a highly reactive secondary radical that causes cell killing DNA damage. Here we characterized bioreductively-activated, hypoxia-selective DNA-strand cleavage by 1,2,4-benzotriazine 1,4-dioxide. We found that one-electron enzymatic activation of 1,2,4-benzotriazine 1,4-dioxide under hypoxic conditions in the presence of the deuterium atom donor methanol-d4 produced non-deuterated mono-N-oxide metabolites. This and the results of other isotopic labeling studies provided evidence against the generation of atom-abstracting drug radical intermediates and are consistent with a DNA-damage mechanism involving release of hydroxyl radical from enzymatically-activated 1,2,4-benzotriazine 1,4-dioxides.

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“…The benzylic radical intermediate is unable to abstract a hydrogen atom from H 2 O (BDE = 118.8 kcal/mol), and instead undergoes hydrogen atom transfer with DMF to form the benzylic C–H bond (BDE = 89.7 kcal/mol). Both the ‐CHO group (BDE = 81.7 kcal/mol) and the ‐CH 3 group (BDE = 89.1 kcal/mol) are the hydrogen donors.…”

Section: C–c Bond Activation With Group 9 Metal Porphyrin Complexesmentioning

confidence: 99%

Carbon–Carbon Bond Activation by Group 9 Metal Complexes

Chan

2019

Eur J Org Chem

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Activation of carbon–carbon bond with transition metal complexes in homogeneous conditions is an emerging field in chemical transformation. The numerous reports in last century have aided the understandings and realization of selective cleavage of carbon–carbon bond in organic molecules, from the viewpoints of the choice of metal, ligand design and substrate scopes. Specifically, this review focuses on the oxidative addition of C–C bond with group 9 transition metal complexes including the rational design from stoichiometric to catalytic transformation from the insight of carbon–carbon and metal‐carbon bond strengths.

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Protodediazoniation of Aryldiazonium Fluoroborates by Dimethylformamide [1]

Cited by 14 publications

References 53 publications

3-Acetoxyquinuclidine as Catalyst in Electron Donor–Acceptor Complex-Mediated Reactions Triggered by Visible Light

3-Acetoxyquinuclidine as Catalyst in Electron Donor–Acceptor Complex-Mediated Reactions Triggered by Visible Light

Isotopic Labeling Experiments That Elucidate the Mechanism of DNA Strand Cleavage by the Hypoxia-Selective Antitumor Agent 1,2,4-Benzotriazine 1,4-Di-N-oxide

Carbon–Carbon Bond Activation by Group 9 Metal Complexes

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