Development of Novel Methodology Using Diazo Compounds and Metal Catalysts

Harada, Shingo

doi:10.1248/cpb.c21-00757

Cited by 13 publications

(13 citation statements)

References 41 publications

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“…Cyclopropanes constitute an important class of reactive compounds with unique structures and properties. Due to their ability to undergo ring-opening/cyclization reactions, cyclopropanes are widely used as precursors or intermediates for numerous applications in organic synthesis. − One of the general methods for cyclopropanation of olefins involves the reaction between olefins and diazoalkanes catalyzed by transition metal complexes. − In particular, diazomethane (CH 2 N 2 ) is used for cyclopropanation as a precursor of methylene. However, the explosiveness and toxicity of diazomethane limit its broader use .…”

Section: Results and Discussionmentioning

confidence: 99%

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

Parfenov

Иванов

Харитонов

et al. 2022

Ind. Eng. Chem. Res.

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Direct oxidation of n-butenes is the preferred but yet unrealized route to methyl ethyl ketone (MEK). At the same time, N 2 O is a promising selective oxidant for conversion of olefins mainly to ketones. In this work, we studied the possibility of producing MEK via the gas-phase noncatalytic oxidation with N 2 O of butene isomers in the C4 refinery stream from catalytic cracking. The oxidation was performed at 573−823 K and a pressure of up to 2 MPa. NMR and gas chromatography methods were used to identify the reaction products. It was shown that N 2 O selectively oxidizes only butenes in the C4 fraction to form nitrogen and carbonyl products, among which MEK is predominant. The reaction proceeds through the 1,3-dipolar cycloaddition of N 2 O to the CC bond of butenes. The proposed method allows obtaining valuable oxygenates without the separation of the C4 fraction and opens a potential way for the rational utilization of waste N 2 O, a powerful greenhouse gas.

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Section: Results and Discussionmentioning

confidence: 99%

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

Parfenov

Иванов

Харитонов

et al. 2022

Ind. Eng. Chem. Res.

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“…Carbene chemistry represents an extremely valuable branch of organic synthesis that has already proven to be a powerful tool for the construction of a wide range of C–C and C–X bonds, − including transformations of pharmaceutical interest. − Over the years, various precursors of carbene intermediates were developed, among which diazo carbonyl compounds stand at the forefront generating this reactive species under thermal and photochemical ,− conditions or in metal-catalyzed reactions. − Most of their applications are, however, limited to stabilized reagents with at least one electron-withdrawing group adjacent to the diazo carbon atom. , In contrast, the safe synthetic use of nonstabilized counterparts requires in situ generation from, for example, hydrazones, − diazirines, , or 1,3,4-oxadiazolines. , …”

Section: Introductionmentioning

confidence: 99%

UV Light Is No Longer Required for the Photoactivation of 1,3,4-Oxadiazolines

et al. 2023

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Carbenes play a key role in a plethora of organic transformations. Although stabilized diazo carbonyl compounds predominate as a source of electrophilic carbenes, the hazardous nature of nonstabilized analogues calls for their in situ generation from stable precursors. Among these, 1,3,4-oxadiazolines serve as diazoalkane surrogates under UV light irradiation. In view of their high stability, diverse reactivities, and straightforward synthesis, milder methodologies for the activation of these compounds that permit the use of UV-light-sensitive substrates are highly valued. Herein, we report the visible-light-induced activation of oxadiazolines by triplet energy transfer catalysis that, in contrast to UVinduced processes, alters their reactivity and enables the generation of carbenes. The formed reactive species react with electron-poor olefins, thereby giving valuable spirocyclopropanes. Mechanistic investigations, both theoretical and experimental, uncover plausible pathways and highlight the importance of the triplet energy transfer steps.

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“…Diazo compounds can generate highly reactive carbenes or metal carbenoid species under thermal, photochemical or transition-metal-catalyzed conditions. [1][2][3][4][5] They have been widely used as versatile synthetic building blocks in numerous reactions [6,7] including 1,3-dipolar cycloaddition, cyclopropanation, the Wolff rearrangement, XÀ H insertion reactions (X = C, O, N, P, S, Si, etc. ), phosphorus or sulfur ylides formation and Pdor triarylborane-catalyzed cross-couplings.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diazo Compounds by Using NaN₃ and Inexpensive SO₂F₂

Yan

Chen

et al. 2022

Eur J Org Chem

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A concise and efficient method was developed in which sodium azide (NaN 3 ) and sulfuryl fluoride (SO 2 F 2 ) were directly employed to synthesize diazo compounds with active methylene compounds. A variety of diazo compounds were produced in good to excellent yields. This protocol avoids the use of organosulfonyl azides, and features atom economy and mild reaction conditions. An alternate method for the synthesis of diazo compounds was provided.

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Development of Novel Methodology Using Diazo Compounds and Metal Catalysts

Cited by 13 publications

References 41 publications

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

UV Light Is No Longer Required for the Photoactivation of 1,3,4-Oxadiazolines

Synthesis of Diazo Compounds by Using NaN₃ and Inexpensive SO₂F₂

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Development of Novel Methodology Using Diazo Compounds and Metal Catalysts

Cited by 13 publications

References 41 publications

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

Gas-Phase Selective Oxidation of Butenes in the C4 Fraction by Nitrous Oxide

UV Light Is No Longer Required for the Photoactivation of 1,3,4-Oxadiazolines

Synthesis of Diazo Compounds by Using NaN3 and Inexpensive SO2F2

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Synthesis of Diazo Compounds by Using NaN₃ and Inexpensive SO₂F₂