The utility of hexachlorodisilane for the deoxygenation of nitrones, 2H-imidazole 1-oxides, 5H-pyrazole 1-oxides, and related N-hydroxy compounds

Hortmann, Alfred G.; Koo, Jachoon; YU, C. C.

doi:10.1021/jo00405a047

Cited by 28 publications

(7 citation statements)

References 3 publications

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“…However, selective mono‐reduction to the corresponding 1‐hidroxybenzimidazole with one equivalent of pinacol could not be achieved. In the same way, 2 H ‐imidazole 1‐oxides such as 9 , as well as triazole N ‐oxides such as 11 , were also efficiently deoxygenated to 2 H ‐imidazole 10 and 2 H ‐1,2,3‐triazole 12 , respectively. Finally, also N,N ‐dimethylaniline N ‐oxide 13 could be deoxygenated to the corresponding aniline 14 , showing that this methodology is also suitable for non heteroaromatic N ‐oxides.…”

Section: Methodsmentioning

confidence: 99%

Molybdenum‐Catalyzed Deoxygenation of Heteroaromatic N‐Oxides and Hydroxides using Pinacol as Reducing Agent

et al. 2017

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A molybdenum-catalyzed deoxygenation of pyridine N-oxides and N-hydroxybenzotriazoles, as well as other azole N-oxides, has been developed using pinacol as an environmentally friendly oxoacceptor. The only by-products are acetone and water making the process a convenient alternative to established protocols in terms of waste generation. The reaction is highly chemoselective and a variety of functional groups are tolerated. The processes are usually very clean allowing the isolation of the pure deoxygenated products after a simple extraction in most cases.

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Section: Methodsmentioning

confidence: 99%

Molybdenum‐Catalyzed Deoxygenation of Heteroaromatic N‐Oxides and Hydroxides using Pinacol as Reducing Agent

et al. 2017

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“…The molecular structures of all the objectives with bond length in Å are shown in Schemes –. Some of these molecules or their analogues have already been reported previously, such as A1–1, A2–1, B2–1, C1–2, E1–1, F1–1, G1, G1–1, G1–2, G2–1, H1, H1–1, H1–2, H2, H2–1, H2–5, H3, I1, I1–1, I1–4, and J1, providing sufficient bases for comparing the calculated and experimental results.…”

Section: Resultsmentioning

confidence: 90%

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study

2016

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N-Oxidization is an important strategy for enhancing the density and energy of energetic materials. Nevertheless, the influence of N-O introduction on molecular stability remains relatively unknown. Thus, the present work comprehensively studied 102 basic N-rich ring structures, including azoles, furazans, and azines, as well as their N-oxides by quantum chemical calculations. The introduction of N-O weakens molecular stability in most cases because the process elongates chemical bonds, decreases ring aromaticity, narrows the gaps between the highest occupied and lowest unoccupied molecular orbitals, and increases the photochemical reactivity. Besides, the easy H transfer to the neighboring O atom, which forms a N-OH isomer in azoles, renders the stabilization by N-oxide introduction ineffective. However, N-oxide introduction can enhance the molecular stability of 1,2,3,4-tetrazine-1,3-dioxide and tetrazino-tetrazine 1,3,6,8-tetraoxide by promoting σ-π separation and relieving lone-pair repulsion. Moreover, the alternate arrangement of positive and negative charges is another factor stabilizing the 1,2,3,4-tetrazine ring by 1,3-dioxidation. Finally, we assess the accessibility of N-oxidized azoles and azines by regarding NO and HO as oxidizers. We find that all the oxidations were exothermic, thermodynamically spontaneous, and kinetically feasible. After an overall evaluation, we propose 19 N-oxides as basic structures for high-energy materials with considerable stability.

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“…[277] Me Me Et 68 [277] Me Et iPr 52 [277] Me t-Bu Me 75 [277] Me t-Bu iPr 47 [277] H Ph iPr 65 [277] H P h P r 5 8 [277] H P h E t 7 2 [277] Me Bn Pr 70 [277] Me Bn Me 68 [277] 40 Reduction of nitrones to afford N,N-dialkylhydroxylamines is effected by sodium borohydride, lithium borohydride, sodium cyanoborohydride, or catalytic hydrogenation. [100,276,[278][279][280][281][282][283][284][285][286][287][288][289][290][291] Thus, lithium aluminum hydride reduction of C-(2-adamantyl)-Nbenzylnitrone gives 2-(N-benzyl-N-hydroxyamino)adamantane (207) in 60% yield (Scheme 71). [279] 1-Hydroxy-3,3-diphenylazetidine (208) can be obtained from sodium borohydride reduction of the corresponding nitrone in 86% yield.…”

Section: Methods 3: Reductive Alkylation Of Oximes With Carboxylic Acidsmentioning

confidence: 99%

Product Class 5: Hydroxylamines

Enders¹,

Schaumann²

2009

Category 5, Compounds With One Saturated Carbon Heteroatom Bond

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The utility of hexachlorodisilane for the deoxygenation of nitrones, 2H-imidazole 1-oxides, 5H-pyrazole 1-oxides, and related N-hydroxy compounds

Cited by 28 publications

References 3 publications

Molybdenum‐Catalyzed Deoxygenation of Heteroaromatic N‐Oxides and Hydroxides using Pinacol as Reducing Agent

Molybdenum‐Catalyzed Deoxygenation of Heteroaromatic N‐Oxides and Hydroxides using Pinacol as Reducing Agent

Influence of N-Oxide Introduction on the Stability of Nitrogen-Rich Heteroaromatic Rings: A Quantum Chemical Study

Product Class 5: Hydroxylamines

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