Azoalkane synthesis by direct oxidation of semicarbazides with copper halide

Heyman, M.; Bandurco, Victor T.; Snyder, James P.

doi:10.1039/c29710000297

Cited by 19 publications

(9 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The next step is the oxidation of the hydrazo moiety by Cu(II), which has been demonstrated to generate Cu(I) species (Figure 4). Formation of isocyanate 18 is proposed based on the study of Heyman et al 29. In this report, the oxidation of alkyl semicarbazides with CuCl 2 was shown to produce isocyanates by the elimination of the diazene group.…”

Section: Resultsmentioning

confidence: 81%

“…Agly peptides feature a 1,2‐dicarbonyl hydrazine motif. The interaction or reaction of Cu(II) salts with hydrazine derivatives such as semicarbazide28, 1,2‐dialkyl semicarbazide29, 1‐phenyl semicarbazide30, or 1,2‐diacyl hydrazines31 has been reported. In this context, the study of Agly peptides stability in the presence of Cu(II) was worth studying.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Selective cleavage of an azaGly peptide bond by copper(II). Long‐range effect of histidine residue

Mhidia

Melnyk

2010

Journal of Peptide Science

View full text Add to dashboard Cite

Several reports have highlighted the interest of replacing Gly, a frequent amino acid within bioactive peptides, by azaGly (Agly) to improve their stability, activity or for the design of prodrugs. Because metal catalysis is increasingly used for tailoring peptide molecules, we have studied the stability of Agly peptides in the presence of metal ions. In this study, we show that Cu(II), unlike other metal ions such as Fe(II), Fe(III), Pd(II), or Pt(II), induces the cleavage of Agly peptides at room temperature and pH 7.3. The cleavage occurred in the absence of an anchoring His residue within the peptide but it was accelerated when this amino acid was present in the sequence. The influence of His residue on the cleavage rate was minimal when His and Agly were adjacent, whereas large effects were observed for distant His residues. The reaction between Cu(II) and Agly peptides induced the formation of Cu(I) species, which could be detected using bicinchoninic acid as a probe. The nature of products formed in this reaction allowed suggesting a mechanism for the Cu(II)-induced cleavage of Agly peptides.

show abstract

Section: Resultsmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Selective cleavage of an azaGly peptide bond by copper(II). Long‐range effect of histidine residue

Mhidia

Melnyk

2010

Journal of Peptide Science

View full text Add to dashboard Cite

show abstract

“…From an aqueous solution of diazabicycloheptane and CuCl 2 , the complex was cleanly deposited at room temperature; decomposition with NH 4 OH then led to 2,3-diazabicycloheptane [103].…”

Section: Oxidations In the Presence Of Copper (Ii) Halidesmentioning

confidence: 99%

Versatile Reactivity and Catalytic Effects of Copper(II) Halides in Organic Syntheses

Csende¹,

Stájer

2005

COC

View full text Add to dashboard Cite

Copper(II) salts are widely applied for the halogenation of aromatic and heteroaromatic systems, the halides. In coupling reactions, CuCl 2 has been used as a catalyst for the benzylation of aromates, the synthesis of alkanes, and the preparation of diacetylenes, cyclohexenones and symmetric biaryls. It has further proved suitable for stereoselective cyclization to lactones, carbon-nitrogen coupling and lactamization, and for the simple preparation of aroylaminohydrazones, the allylic amination of olefins, the carbonylation of alkylamines, and heterocyclizations to pyrrolidinones, pyridinones, pyrroles and dihydrofurans. The dehydrogenation of carbocycles and heterocycles can be used in the synthesis of gibberelic acid, for the aromatization of oestrogen derivatives and for the conversion of dihydrouracils to uracils. From tetrahydroisoquinolines, dihydro derivatives have been formed, while dihydropyridazines in the presence of Cu(II) salts yield pyridazines. Similarly, the oxidations of cyclohexane, adamantane and methylcatechol to benzoquinone, and amines to nitriles have been performed. The conversion of aldehydes to nitriles and benzyl radical cyclizations to butyrolactones have been achieved. Protection and deprotection, and various other Cu(II) halide-mediated reactions are also discussed.

show abstract

“…C2,H220,S2 requires C, 61.49; H, 5.75; S, 16.43%); v,,,,(CHCI,) 1625 (m, C=C) and 1 317 and 1 143 (s, SO,); G,(CDCl,) 1.49 (4 H, br t, J 6 Hz), 2.25 (4 H, br q, J 6 Hz), 6.33 (2 H, dt, J 15,1.5 Hz), 6.95 (2 H, dt, J 15, 7 Hz), 7.58 (6 H, m), 7.88 (4 H, d, J 8 Hz); mi; (e.i.) 390 ( M + , l%), 249 (21), 195 (19), 143 (IS), 125 (78), 107 (loo), 77 (64); mjz ( c i , CH,) 394 (l%), 393 (4), 392 (9), 391 (39), and 390 (0).…”

Section: [78-2h2]-cis-bicyclo[420]octane-the Above Experimentsmentioning

confidence: 99%

Deazetation of a bicyclic azo compound: resolution of a stereochemical ambiguity and conformational analysis of a biradical

Samuel¹

1989

J. Chem. Soc., Perkin Trans. 1

View full text Add to dashboard Cite

Azoalkane synthesis by direct oxidation of semicarbazides with copper halide

Cited by 19 publications

References 0 publications

Selective cleavage of an azaGly peptide bond by copper(II). Long‐range effect of histidine residue

Selective cleavage of an azaGly peptide bond by copper(II). Long‐range effect of histidine residue

Versatile Reactivity and Catalytic Effects of Copper(II) Halides in Organic Syntheses

Deazetation of a bicyclic azo compound: resolution of a stereochemical ambiguity and conformational analysis of a biradical

Contact Info

Product

Resources

About