Preparation of trialkyltriazenes. A comparison of the nitrogen-nitrogen bond rotation in trialkyltriazenes and aryldialkyltriazenes by variable temperature carbon-13 NMR

Sieh, David H.; Wilbur, David J.; Michejda, Christopher J.

doi:10.1021/ja00531a033

Cited by 49 publications

(27 citation statements)

References 8 publications

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“…Trialkyl triazenes have received moderate attention in the literature as possible antitumor agents 45. Although trialkyl triazenes were prepared by Dimroth46 almost a century ago, a general synthesis of these compounds was only accomplished within the last 30 years 47. Proteolytic decomposition to the alkyl diazonium species has been demonstrated using pH‐buffered solutions, however, their practical effectiveness is hampered by instability.…”

Section: Medical Applications Of Triazenesmentioning

confidence: 99%

Triazenes: A Versatile Tool in Organic Synthesis

Kimball

Haley

2002

Angew. Chem. Int. Ed.

283

149

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Triazenes (RN=N-NR'R") are a class of compounds that hold much promise in preparative chemistry as they are reactive groups which are both stable and adaptable to numerous synthetic transformations. Useful to scientists in pharmacology, total synthesis, polymer technology, and the construction of novel ring systems, to name a few areas, triazenes also have a tendency to surprise chemists with new reactions and increasing applicability. This review highlights some of the recent advances and diversity possible with these types of systems.

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Section: Medical Applications Of Triazenesmentioning

confidence: 99%

Triazenes: A Versatile Tool in Organic Synthesis

Kimball

Haley

2002

Angew. Chem. Int. Ed.

283

149

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“…[8] Trialkyltriazenes have been prepared by the reaction of aliphatic azides with organolithium compounds, followed by alkylation with organohalides (Scheme 1 b). [9] These standard procedures have an important shortcoming: triazenes with alkynyl or alkenyl substituents in the 1-position are difficult to access because the required starting materials are highly unstable. 1-Azido-1alkynes, for example, decompose at low temperatures and the first spectroscopic characterization of such a compound was only achieved recently.…”

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confidence: 99%

“…An optimization of the reaction conditions for trialkyltriazenes was not undertaken because these compounds can be prepared by alternative procedures. [9] The reaction of lithium dialkylamides with N 2 O was examined in more detail to obtain information about the mechanism of the reaction. In the literature, one finds only sparse data about this type of reaction.…”

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confidence: 99%

Synthesis of Triazenes with Nitrous Oxide

et al. 2014

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Triazenes are valuable compounds in organic chemistry and numerous applications have been reported. Furthermore, triazenes have been investigated extensively as potential antitumor drugs. Here, we describe a new method for the synthesis of triazenes. The procedure involves a reagent which is rarely used in synthetic organic chemistry: nitrous oxide (N2 O, "laughing gas"). Nitrous oxide mediates the coupling of lithium amides and organomagnesium compounds while serving as a nitrogen donor. Despite the very inert character of nitrous oxide, the reactions can be performed in solution under mild conditions. A key advantage of the new procedure is the ability to access triazenes with alkynyl and alkenyl substituents. These compounds are difficult to prepare by conventional methods because the required starting materials are unstable. Some of the new alkynyltriazenes were found to display high cytotoxicity in in vitro tests on ovarian and breast cancer cell lines.

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“…cycloadditions, a mixture of linchpin and arynophile was treated with MeLi at −78°C for 10 min in THF, followed, in turn, by warming to 0°C for 10 min before the silyl group was removed. However, with benzylazide, an arynophile known to react with alkyl lithium (26), linchpin 34 was first reacted with MeLi in Et 2 O for 5 min at −78°C. In turn, benzyl azide was then added in THF at −78°C and allowed to react for 2 min exploiting a solvent, temperature, and reaction time known to initiate and complete the Type II ARC/benzyne reaction sequence.…”

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confidence: 99%