Trans-1,4-Diamino

Benzil-bis-[phenylimin] kann durch Reduktion in DMF mit Tetraalkylammoniumsal-zen bei Gegen wart von Methylhalogeniden zu Gemischen wechselnder Zusammensetzung von cis- und trans-1,2-Diamino-, 1,2-Bis-[methylamina]- bzw. 1,2-Bis-[dimethylamino]-l, 2-diphenyl-athen umgesetzt werden (vgl. S. 616)5. 

The reductive amination of ketones can be carried out under hydrogen pressure in the presence of palladium catalysts. However, if enantiopure Q -aminoketones are used, partial racemization of the intermediate a-amino imine can occur, owing to the equilibration with the corresponding enam-ine [102]. Asymmetric hydrogenation of racemic 2-amidocyclohexanones 218 with Raney nickel in ethanol gave a mixture of cis and trans 1,2-diamino cyclohexane derivatives 219 in unequal amounts, presumably because the enamines are intermediates, but with excellent enantioselectivity. The two diastereomers were easily separated and converted to the mono-protected cis- and trans- 1,2-diaminocyclohexanes 220. The receptor 221 has been also synthesized by this route [103] (Scheme 33). 

Silylation-amination of 6-acetoxymethyl-5-deazapterine 265 with NH3, HMDS 2, and TsOH for 120 h at 155-160°C in an autoclave affords, after subsequent trans-silylation with boiling methanol, the diamino compound 266 in 74% yield [76]. Silylation-amination-cychzation of the substituted 4-quinolone 267 gives the alkaloid isoaptamine hydrochloride 268 in 51% yield [77, 78] (Scheme 4.30). 

Bis(diamino)alanes (R2N)2A1H were used for the hydroalumination of terminal and internal alkenes [18, 19]. TiCb and CpjTiCb are suitable catalysts for these reactions, whereas CpjZrCb exhibits low catalytic activity. The hydroaluminations are carried out in benzene or THF soluhon at elevated temperatures (60°C). Internal linear cis- and trans-alkenes are converted into n-alkylalanes via an isomerization process. Cycloalkenes give only moderate yields tri- and tetrasubstituted double bonds are inert. Hydroaluminahon of conjugated dienes like butadiene and 1,3-hexa-diene proceeds with only poor selechvity. The structure of the hydroaluminahon product of 1,5-hexadiene depends on the solvent used. While in benzene cyclization is observed, the reaction carried out in THF yields linear products (Scheme 2-10). 

The macrocyclic ligand 6,13-diamino-6,13-dimethyl-1,4,8,11 -tetra-azacyclotetradecane (diammac), illustrated in Scheme 5 for the two cis and trans conformations, is properly suited to fulfil the requirement of six donor atoms to satisfy the Cr(III) hexacoordination. In fact, in addition to the four central N atoms it has two amine groups (a sort of head and tail, from which the name scorpiands is given to these ligands). 

The question then arises if a regioselective opening of a 2,3-rraMS-epoxy carboxamide derived from aldonic acids would occur. The 2,5-di-O-tosyl-D-ribono-1,4-lactone (62) (Scheme 13) was used to find an answer to this question. If treated with ammonia, the 2,5-diamino-2,5-dideoxy-D-ribono-1,5-lactam (63) was obtained as the only product [79]. The NMR spectra of the reaction mixture showed the formation of the diepoxy amide A which was opened at C-5 by ammonia. In this case no internal lactamization could occur, due to the trans 2,3-epoxy group in B (Scheme 13). Thus, a regioselective opening of an acyclic 2,3-epoxy carboxamide took place at C-2. The reaction was complete within 6 days. 

H, NOz H3/Pt02/H,C-C00H 20-25=, 3,5 h trans-l, 4-Diamino-cyclo-hexan 98 7... 

In ahnlicher Weise erhalt man z.B. aus dem Aziridin 1 uber trans-2-Amino-l-azido-7-brom-tetralin trans-1,2-Diamino-7-brom-tetralinx. 

Trans-diethylenediamino-diammino-cobaltic Nitrate, [Co en2 (XH3)2](N03)3, is formed when 1-, 2-dinitrito-diethylenediamino-cobaltic nitrate, [Co en2(N02)2]X03, is heated with nitric acid. It is first converted into the dinitrato-sait, which separates in dark red triclinie crystals. This then reacts with liquid ammonia, forming diethylene-diamino-diammino-eobaltic nitrate together with a small quantity of the ci.s-salt. The nitrate forms a red viscid syrup which is soluble in water and on the addition of potassium iodide yields the iodide, which separates from hot -water in small orange-yellow crystals or refractive rhombic plates. 

Pl-DAT = polyimide-3,5-diamino-1,2,4-triazole support. j Ratio tran s/cis 69/31. k Side product 18% of f-butyl benzoate. 

Aziridinyl ketones can be synthesized from unsaturated carbonyls using a series of other methods. For example, azabicyclo[4.1.0]heptanone 27 was obtained from cyclohexenone 25 in its reaction with TV-bromotoluenesulfona-mide sodium salt 33 [49] (Scheme 1.10). The reaction of chalcone with N-chlorotoluenesulfonamide in the presence of silver nitrite is described in [50]. Trans-Aziridinyl ketone 18 was synthesized by reacting chalcone 22 with N,N-diamino-l,4-diazoniabicyclo[2.2.2.]octane dinitrate 34 and sodium hydride in 2-propanol [30, 51]. Aziridinyl ketones can be obtained in the reaction of a -unsaturated ketones with A,A-dichlorosulfonamines [52] and with amines in the presence of lead tetraacetate and trifluoroacetic acid [53] or in the presence of triethylammonium acetate under electrochemical reaction conditions [54]. 

Bailey, N. A., Fenton, D. E., Moody, R., etal., Complexes of ligands providing endogenous bridges A. copper(II) complexes of macrocyclic Schiff-bases derived from 2,6-diacetylpyridine and l,N-diamino-N -hydroxyalkanes (N,N = 3,2 - 4,2 - and 5,3) - synthesis, properties, and structures. J. Chem. Soc., Dalton Trans. 1987, 2519-2529. 

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