Nitrogen-bonded Derivatives

Tetradentate Cu, Pt and Pd complexes of the l,2-bis(thiosemicarbazone) derived from 3-deoxy-D-eryrhro-hexos-2-ulose have been prepared, and some sugar analogues of cisplatin which incorporate a mono-N-sugar-substituted ethylene diamine unit have been synthesized.  

Dieguez, O. Pamies, A. Ruiz, S. Castillon and C. Qaver, Tetrahedron Asymmetry, 2000,11,4701. 

Vieira DeAlmeida, E. Teixeira Cesor, A.P. Soares Fontes and E. de Castro Antunes Felicio, J. Carbohydr. Chem., 2000,19,323. 

Some oxorhenium(V) complexes of 2, 3 -diamino-2, 3 -dideoxy-nucleosides have been prepared as inhibitors of purine specific ribonuclease and other 

Huixin, A. Vasella and P. Weiss, Helv. Chim. Acta, 1996,79,1757. 

Kavenova and I. Rosenberg, Collect. Czech. Chem. Commun., 1996, 61, S76 Chem. Abstr., 1996,125, 329 231). 

Kovacs, J. Gyarmati, L. Somak and K. Micskei, Tetrahedron Lett., 1996, 37, 1293. 

Robina, F. Lopez-Barba and J. Fuentes, Synth. Common., 1996,26, 2847. 

D-glucitol have been found to bind to DNA but not to show anti-34 

Reaction of SnMe2Cl2 and SnPh2Cl2 with adenine and some derivatives in methanol gave complexes with the structures 

SnMe2Cl2(adenine)2 and SnPhCl2(0H)(Adenine)2 thought to involve N-7 of the bases.Treatment of Inosine and guanosine with palladium chloride in acid gave a set of complexes 

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Tetramesityliridium reacts with nitric oxide by coupling two nitric oxide molecules foiming the hyponitrite complex [Ir(mesityl)4(p-ONNO-x2o) 93 Sulphur dioxide induces insertion of a caibonyl group into an intermediate iridium - nitrogen bond derived from a benzothiazole 2-thiolate ligand Scheme 6,). The product has been structurally characterised. ... 

Structural parameters and interatomic distances derived from electron diffraction (7) (77JST(42)l2i) and X-ray diffraction (8) studies (76AX(B)3178) provide unequivocal evidence that pyrazine is planar with >2a symmetry. There is an increased localization of electron density in the carbon-nitrogen bonds, with carbon-carbon bonds being similar in length to those in benzene. ... 

Many azo dyes, such as tartrazine (Section 4.04.4.1.3), are susceptible to reduction by bacterial reductases in the intestinal flora. Azo reduction is believed to proceed through a hydrazo intermediate that undergoes subsequent reductive cleavage of the nitrogen-nitrogen bond to yield the arylamine derivatives (B-80MI40406). 

The polar tellurium(II)-nitrogen bond is readily susceptible to protolysis by weakly acidic reagents. Eor example, the reaction of [Te(NMe2)2]oo with two equivalents of Ph3CSH produces the monomeric thiolato derivative Te(SCPh3)2. Alkynyl tellurides may be prepared by the reaction of terminal acetylenes with arenetellurenamides (Eq. 10.13). ... 

To establish the nature of the carbon-nitrogen bond of the carbohydrate-L-asparagine unit in glycoproteins, treatment of the synthetic derivatives 5 and 211 with hydrochloric acid was first studied in... 

The formation of 2H-pyrroles (21) and a pyrrole derivative (22) from the reaction of 3-phenyl-2//-azirines and acetylenic esters in the presence of molybdenum hexacarbonyl is intriguing mechanistically (Schemes 24, 25).53 Carbon-nitrogen bond cleavage must occur perhaps via a molybdenum complex (cf. 23 in Scheme 26) but intermediate organometallic species have not yet been isolated.53 Despite the relatively poor yields of 2H-pyrrole products, the process is synthetically valuable since the equivalent uncatalyzed photochemical process produces isomeric 2H-pyrroles from a primary reaction of azirine C—C cleavage54 (Scheme 24). 

Figure 17.18 The Staudinger ligation reaction uses a modified phosphine derivative containing an electrophilic group that acts as a trap for the nucleophilic nitrogen in the intermediate aza-ylide. The resultant shift yields an amide bond derivative between the phosphine-containing molecule and the azide-containing molecule.

An important variant for transition metal-catalyzed carbon-nitrogen bond formation is allylic substitution (for reviews, see1,la lh). Nucleophilic attack by an amine on an 7r-allyl intermediate, generated from either an allylic alcohol derivative,2 16,16a 16f an alkenyloxirane,17-19,19a-19d an alkenylaziridine19,19a 19d, or a propargyl alcohol derivative,21,21a 21d gives an allylic amine derivative. 

Heats of formation can be derived by reversing the Pauling definition of electronegativity, but empirical corrections are needed to allow for extra strength of multiple oxygen or nitrogen bonding, as in... 

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