Nitrogen-Rich Mesoionic Compounds from 1,3-Diaryl-5-chlorotetrazolium Salts and Nitrogen Nucleophiles − Synthesis and Properties of 1,3-Diaryl-5-azidotetrazolium Salts

Araki, Shuki; Yamamoto, Kaori; Yagi, Misako; Inoue, Tomoko; Fukagawa, Hiroyo; Hattori, Hiromi; Yamamura, Hisao; Kawai, Maki; Butsugan, Yasuo

doi:10.1002/(sici)1099-0690(199801)1998:1<121::aid-ejoc121>3.0.co;2-5

Cited by 19 publications

(3 citation statements)

References 30 publications

(3 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our previous work demonstrated that carbene 1b has a nucleophilic nature and hence is best expressed by the singlet structures A and B . For example, although the attempted reactions with alkyl halides or carbonyl compounds were unsuccessful, 1b reacts readily with nitrogen electrophiles such as benzenediazonium and azidotetrazolium salts [4, 5]. Here, we report further reactions of 1b with electron‐deficient tetrazine and alkene electrophiles.…”

Section: Introductionmentioning

confidence: 92%

“…These carbenes are easily prepared by deprotonation of the corresponding 1,3‐disubstituted tetrazolium salts 2a , 2b with a base at low temperature [3, 4]. Alternatively, 1b can also be generated by the reaction of 5‐azido‐1,3‐diphenyltetrazolium salt with sodium azide [5]. Carbene 1 is thermally labile; upon warming to room temperature, 1 undergoes a ring‐opening to give 3‐cyanotriazene.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Mesoionic carbenes: Reactions of 1,3‐diphenyltetrazol‐5‐ylidene with electron‐deficient alkenes, and synthesis and catalytic activities of the (tetrazol‐5‐ylidene)rhodium(I) complexes

Araki

Yokoi

Sato

et al. 2009

Journal of Heterocyclic Chem

Self Cite

View full text Add to dashboard Cite

in Wiley InterScience (www.interscience.wiley.com).The reactions of 1,3-diphenyltetrazol-5-ylidene, a rare example of mesoionic carbenes, with electrondeficient unsaturated compounds were studied. The carbene reacted with dimethyl 1,2,4,5-tetrazine-3, 6-dicarboxylate to give a 5-tetrazoliomethylide, together with hydrazine derivatives. The reaction with tetracyanoethylene gave another methylide in low yield. On the contrary, the reactions with weaker electrophiles, such as 3,6-diphenyl-1,2,4,5-tetrazine, fumalonitrile, N-phenylmaleimide, and dimethyl acetylenedicarboxylate, did not give any coupling products, but gave phenylated products and/or Michael addition products via the degradation of the 1,3-diphenyltetrazole ring. Novel mesoionic monoand bis(carbene)-rhodium(I) complexes were synthesized and the structures were characterized by X-ray crystallography. Their catalytic activities for the decarbonylative addition reaction of benzoyl chloride to ethynylbenzene were investigated.

show abstract

Section: Introductionmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Mesoionic carbenes: Reactions of 1,3‐diphenyltetrazol‐5‐ylidene with electron‐deficient alkenes, and synthesis and catalytic activities of the (tetrazol‐5‐ylidene)rhodium(I) complexes

Araki

Yokoi

Sato

et al. 2009

Journal of Heterocyclic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…The most interesting and less examined 5-aminotetrazole derivatives are tetrazolium-5-aminides, which can be depicted as 4 by analogy with other mesoionic tetrazoles [11,12]. The first representatives of tetrazole-5-aminides were reported in the 1950s [13,14], whereas next publications were appeared only five decades later, being devoted to the synthesis and photochemistry of 1,3-diaryltetrazolium-5-aminides [15][16][17][18][19][20][21]. NMR studies of a few tetrazole-5-aminides were carried out as a part of studies of mesoionic compounds [22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

Budevich¹,

Войтехович²,

Zuraev³

et al. 2021

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Tetrazolium-5-aminides have been prepared by the tert-butylation of 5-aminotetrazole and its N-methyl derivatives by the t-BuOH/HClO4 system followed by the treatment of the tetrazolium salts by alkali. The mesoionic compounds have been found to show a higher reactivity of the exocyclic N atom in comparison with 5-aminotetrazoles. The compounds reacted with 1,2-dibromoethane and 5-(methylsulfonyl)-1-phenyl-1H-tetrazole with substitution of bromine and methylsulfonyl groups giving the corresponding tetrazolium salts or conjugate aminides. The obtained mesoionic tetrazoles have been characterized by elemental analysis, FTIR, NMR, and UV–vis spectroscopy, TGA/DSC analysis and for 1,3-di-tert-butyltetrazolium-5-aminide, its N,N’-ethylene-bridged bis-derivative and (1,3-di-tert-butyl-1H-tetrazol-3-ium-5-yl)(1-phenyl-1H-tetrazol-5-yl)amide by single crystal X-ray analysis. The structural and spectral features of the tetrazolium-5-aminides are discussed by using quantum-chemical calculations.

show abstract

Stable Mesoionic N‐Heterocyclic Olefins (mNHOs)

2020

View full text Add to dashboard Cite

We report a new class of stable mesoionic N‐heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground‐state structure cannot be described through an uncharged mesomeric Lewis‐structure, thereby structurally distinguishing them from traditional N‐heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′‐diaryl‐1,2,3‐triazolium and N,N′‐diaryl‐imidazolium salts, respectively. In their reactivity, they represent strong σ‐donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.

show abstract

Nitrogen-Rich Mesoionic Compounds from 1,3-Diaryl-5-chlorotetrazolium Salts and Nitrogen Nucleophiles − Synthesis and Properties of 1,3-Diaryl-5-azidotetrazolium Salts

Cited by 19 publications

References 30 publications

Mesoionic carbenes: Reactions of 1,3‐diphenyltetrazol‐5‐ylidene with electron‐deficient alkenes, and synthesis and catalytic activities of the (tetrazol‐5‐ylidene)rhodium(I) complexes

Mesoionic carbenes: Reactions of 1,3‐diphenyltetrazol‐5‐ylidene with electron‐deficient alkenes, and synthesis and catalytic activities of the (tetrazol‐5‐ylidene)rhodium(I) complexes

Mesoionic tetrazolium-5-aminides: Synthesis, molecular and crystal structures, UV–vis spectra, and DFT calculations

Stable Mesoionic N‐Heterocyclic Olefins (mNHOs)

Contact Info

Product

Resources

About