Diamines from aziridines

The 1,2-diamines 41 (R = C6H13, PhCH2 or 4-MeOC6H4CH2) result from the action of trimethylamine A -oxide on the aziridine 40 in the presence of lithium iodide and Fe3(CO)i271. 

Alkylation of flra-chloroaniline (13-1) with 2,2,2-triiluoroethyl trichloromethyl-sulfonate affords the corresponding trifluroethylated derivative (13-2). Reaction of the anion from that with aziridine proper leads to the formation of the diamine (13-3). Acylation of that compound with ortfio-fluorobenzoyl chloride (13-4) proceeds to... 

Lew and Kim [66] recently synthesized a sulfide isostere of carbocyclic influenza neuraminidase inhibitor 268, moving from trityl protected aziridine 266, in turn prepared from (-)-quinic acid 159 (Scheme 43). Ring opening of 266 with 1-propanethiol promoted by BF3 etherate, followed by acetylation, gave sulfide 267 which was finally hydrogenated to diamine 268, in a good chemical yield. As the authors expected, mercapto-derivative 268 resulted to be a strong inhibitor of... 

The paUadium-promoted vicinal diamination of alkenes can be achieved according to Scheme 39 the example chosen illustrates how the mechanism and stereochonistry were determined. The independent synthesis of (36) from a qualemized aziridine is also notewordiy. Yields are 60-87% from ter-... 

The use of im-butyl /V./V-dichlorocarbamate allows the preparation of the corresponding A -Boc-protcctcd amines, from which the free amines can be conveniently obtained by mild acidic treatment. The addition to indene, and 1,2-dihydronaphthalene and benzopyran derivatives gave exclusively the tram-adducts, from which amines, diamines, aziridines, and oxazo-lidinones were in turn prepared79. 

The more thoroughly developed salen-based catalysts have also been studied in the context of aziridination, albeit with limited success. While Burrows observed no measurable enantioselection in the aziridination of styrene derivatives using simple chiral (salen)Mn catalysts derived from 1,2-phenylethylenedi-amine [14], Katsuki encountered some success (up to 28% ee in the azidination of styrene) with more complex derivatives of the same diamine [15]. Substantially improved enantioselectivities were observed with a less hindered diamine backbone associated with highly optimized chiral salicylide elements. Thus, up to 94% ee has been obtained in the aziridination of styrene with a 2,3-diaminob-utane-derived catalyst (Scheme 6) [16]. Incorporation of catalytic levels of a py-... 

Hazardous properties of some of the aliphatic amines (including diamines, triamines, and aziridines) are presented in Table 8.1. Amines in general, as mentioned earlier, are strongly caustic and can injure the cornea upon direct contact. Skin contact can cause burns, which may vary from severe to second degree or to mild, depending on the carbon chain length. The toxicity is low to moderate. The flammability decreases with an increase in the carbon number. The reactivity of these compounds, in general, is low. Outlined in Table 8.1 are some of the amines used commercially that are hazardous. 

Some of the more important reactions of the aziridines cire set out in the following equations. The v/c-diamine can also be prepared from an epoxide by successive reaction with sodium azide, methane-sulphonyl chloride, sodium azide and hydrogen/ platinum. 

This methodology has also been employed for the preparation of tetradentate ligands by exchanging the primary amines for C2-symmetric primary diamines (eq 4). For example, from (/ ,/ -1,2-diamino-1,2-diphenylethane, diastereomeric ligand B was obtained in 84% yield. These aromatic amines are sufficiently reactive to open the aziridine ring. Due to steric hindrance, no further reaction of the secondary amine moieties with (5)-A -trifluoromethylsulfonyl-2-isopropylaziridine was observed. This tetradentate ligand was inferior to his(sulfonamides) as catalyst... 

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