Olefin vicinal diamines

Nitrogen-transfer reactions of osmium imido species lead to cis diamines or amino alcohols. Reaction of 0s02(N-/-C4H9)2 [63174-13-0] with olefins produces vicinal diamines after reductive cleavage. Catalytic oxyamination of olefins using chloramine-T or AJ-chlor-AJ-argenocarbamates yields vicinal hydroxy toluenesulfonamides (112) or carbamates (113), respectively, which maybe deprotected to vicinal amino alcohols. 

He also pioneered the osmium-catalyzed vicinal aminohydroxylation reaction (AH), where imido osmium complexes react with olefins to form p-aminoalcohols [18]. Closely related to the DH and AH reactions is the amination of olefins leading to vicinal diamines, which was explored by Sharpless [19, 20] and Muniz [21, 22]. 

Diamines.- The preparation of vicinal diamines by functionalisation of olefins remains an area of active research interest. Full details concerning a previously reported synthesis of vic-primary diamines via -bromosuccinimide-mediated addition of cyanamide to unactivated double bonds followed by formation and subsequent hydrolysis of a 2-ethoxyimidazoline have been published. 

Other strategies have been followed to observe palladium-catalyzed diaminations of olefins. The diaminations of dienes have been conducted with ureas, and the use of this reagent leads to the 1,2-, rather than 1,4-, functionalization of the diene (Equation 16.126). The use of an aziridinone as reagent in the presence of olefin and a palladium catalyst also leads to the diamination of conjugated dienes to form precursors to vicinal diamines (Equation 16.127). ... 

The regiospecific C-alkylation of primary benzylamines cf. Vol. 4, p. 174) has now been simplified by the use of a solid-liquid phase-transfer system. Vicinal diamines are not easily prepared directly from olefins, and although two new methods were recently reported (cf. Vol. 3, p. 170 and Vol. 4, p. 175) these have not been applicable to the preparation of primary diamines. A new method for this transformation involves the use of the cyclopentadienylnitrosyl-cobalt dimer (7), and is considered to be of general applicability. Some stereoselectivity was observed. 

Olefins can be transformed stereospecifically into vicinal diamines (23) by an aminopalladation-oxidation sequence (Scheme 16) using oxidants such as bromine, m-chloroperbenzoic acid, and iV-bromosuccinimide. Although this diamination procedure has limitations, the results are nevertheless useful since vicinal diamines are not easily prepared from olefins by other methods. 

Some instances of incomplete debromination of 5,6-dibromo compounds may be due to the presence of 5j5,6a-isomer of wrong stereochemistry for anti-coplanar elimination. The higher temperature afforded by replacing acetone with refluxing cyclohexanone has proved advantageous in some cases. There is evidence that both the zinc and lithium aluminum hydride reductions of vicinal dihalides also proceed faster with diaxial isomers (ref. 266, cf. ref. 215, p. 136, ref. 265). The chromous reduction of vicinal dihalides appears to involve free radical intermediates produced by one electron transfer, and is not stereospecific but favors tra 5-elimination in the case of vic-di-bromides. Chromous ion complexed with ethylene diamine is more reactive than the uncomplexed ion in reduction of -substituted halides and epoxides to olefins. ... 

In 1994, Hanessian and co-workers [50] reported the first examples of metal-free three-dimensional triple-stranded helicates through spontaneous self-assembly of chiral C2-symmetrical diols and chiral C2-symmetrical diamines. The initial observation resulted from the utilization of enantiopure C2-symmetrical vicinal trans-1,2-diaminocyclohexane [51,52] as ligands in the asymmetric dihydroxylations of olefins [53] and as reagents for asymmetric synthesis [54], When equimolar amounts of (5,5)-frfl x-l,2-diaminocyclohexane (28) and its (i ,i )-enantiomer (29) were individually mixed with (5,5)-frfl x-l,2-cyclohexanediol and heated in refluxing benzene, crystals of the respective supraminol complexes 28 30 and 29 30 were formed quantitatively (Scheme 12). This was the physical basis for the separation of racemic diols with tr[Pg.104]

Sharpless and coworkers have reported a new series of reagents for allylic amination of olefins,79-5 vicinal oxyamination of olefins,76 and 1,2-diamination of 1,3-dienes.77... 

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