Isolation and reactivity of an elusive diazoalkene

Antoni, Patrick W.; Golz, Christopher; Holstein, Julian J.; Pantazis, Dimitrios A.; Hansmann, Max M.

doi:10.1038/s41557-021-00675-5

Cited by 68 publications

(99 citation statements)

References 42 publications

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“…This then apparently undergoes apair of fast competing subsequent reactions,n amely N 2 loss to give the oxaborirane system of 18 and af ragmentation reaction with concomitant H-migration to give the diazoalkane product 19.T he later pathway may be regarded as ar ather unusual reaction. [21] We investigated if the alleged intermediate 17 might become observed by performing the reaction at variable temperature,but that was not the case.However,we found some temperature and solvent dependencyofthe ratio of the products 18 and 19.A tr oom temperature in toluene a 18:19 mixture of ca. 5:3was found.…”

Section: Methodsmentioning

confidence: 99%

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

et al. 2021

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The synthesis of element À carbon double bonds is of great importance for the development and understanding of reactive p-bonded systems in chemistry.T he seven-membered heterocyclic system 4b is readily made by internal CÀH activation at apendent isopropyl methyl group of the respective [(IPr)C 6 F 5 BH] + borenium ion. Subsequent deprotonation with the IMes carbene gives the neutral cyclic boraalkene system 5b.T he B = Cd ouble bond in compound 5b adds carbon dioxide,C S 2 ,s ulfur dioxide,p henyl isocyanate,a n acetylenic ester or two NO molecules to give the corresponding four-membered ring annulated heterocycles.W iths ulfur or selenium 5b gives the respective three-membered ring systems. N 2 Oreacts with 5b to give amixture of the related oxaborirane 18 and au nique [B]OH containing diazoalkane product 19.

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Section: Methodsmentioning

confidence: 99%

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

et al. 2021

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“…The reactivity of the triazole-derived mesoionic N-heterocyclic olefin with various small molecules such as N 2 O ( 154 ), CO, and CS 2 has also been demonstrated by the same research group. 130 , 131 …”

Section: Main Group Educts Of Micsmentioning

confidence: 99%

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Maity

Sarkar

2021

JACS Au

106

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Mesoionic carbenes (MICs) of the 1,2,3-triazolylidene type have established themselves as a popular class of compounds over the past decade. Primary reasons for this popularity are their modular synthesis and their strong donor properties. While such MICs have mostly been used in combination with transition metals, the past few years have also seen their utility together with main group elements. In this paper, we present an overview of the recent developments on this class of compounds that include, among others, (i) cationic and anionic MIC ligands, (ii) the donor/acceptor properties of these ligands with a focus on the several methods that are known for estimating such donor/acceptor properties, (iii) a detailed overview of 3d metal complexes and main group compounds with these MIC ligands, (iv) results on the redox and photophysical properties of compounds based on MIC ligands, and (v) an overview on electrocatalysis, redox-switchable catalysis, and small-molecule activation to highlight the applications of compounds based on MIC ligands in contemporary chemistry. By discussing several aspects from the synthetic, spectroscopic, and application point of view of these classes of compounds, we highlight the state of the art of compounds containing MICs and present a perspective for future research in this field.

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“…[32][33][34][35] Besides these NHOs, Hansmann and co-workers recently introduced a super nucleophilic mesoionic N-heterocyclic olefin (mNHO) 1 containing a polarised exocyclic double bond. 36,37 The Tolman electronic parameter (TEP) of 1 (2023 cm -1 )suggests that mNHO 1 has the strongest donor property compared to NHC (2051 cm -1 ), NHOs (2024-2031 cm -1 ) and aNHC (2039 cm -1 ), (Scheme 1a). 36 Moreover, the theoretical calculations predicted that the mNHO (1) possessing the highest proton affinity value of 293.3 kcal/mol is likely to be the strongest nucleophile among earlier reported N-heterocyclic olefins (NHOs) whose proton affinity values lie in the range of 262-282 kcal/mol (Scheme 1b).…”

Section: Introductionmentioning

confidence: 99%

Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO₂ for consecutive N-methylation of amines

2021

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Isolation and reactivity of an elusive diazoalkene

Cited by 68 publications

References 42 publications

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO₂ for consecutive N-methylation of amines

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Isolation and reactivity of an elusive diazoalkene

Cited by 68 publications

References 42 publications

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

Formation and Cycloaddition Reactions of a Reactive Boraalkene Stabilized Internally by N‐Heterocyclic Carbene

Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO2 for consecutive N-methylation of amines

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Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO₂ for consecutive N-methylation of amines