β‐Funktionalisierte Hydrazine aus N‐Phthalimidoaziridinen und ihre hydrogenolytische N,N‐Spaltung zu Aminen

Abstract

The three N-phthalimido-aziridines 1-3 were reacted with phenol, thiophenol, aniline, p-toluenesulfonic acid, and H,O in selected combinations. These nucleophiles opened the 3-membered ring to yield the N-phthalimidoamines 4 a 4 , 5 a 4 , 6a-2, and 6e; all these products (except the carbinol 6e) carry an aryl-substituted functional group on the C-atom vicinal to the N-substituent. Hydrazinolysis of 4,5,6a+, and 6e afforded the 8-functionalized hydrazines 7, 8, 9a-2, and 9e. The reducing medium Raney-NilN'H, transformed 4, 5, 6a+, and 6e to the p-functionalized arnines 10, 11, 12a-c, and 12e. By a study with the hydrazide 6a and the hydrazine 9a, it was shown that the N,N-cleavage is a catalytic hydrogenolysis by H, generated from N2H, with Raney-Ni and that it does not take place on the hydrazide 6, but rather on the hydrazine 9, generated as intermediate from 6 with N'H,.Spectroscopic data confirmed that the conversions of 1-3 to 44 occurred exclusively with inversion and that the resulting configurations remained fully intact during the transformations of 4 5 , and 6 (via 7,8, and 9) to 10, 11, and 12, respectively.Inversion entstanden N-Phthalimido-amine4)'): aus dem cis-Aziridin 1 selektiv die threo -Produkte 4 a 4 (6&87 %), aus dem trans-Aziridin 2 die erythro -Produkte 5 a 4 (5685 %)

Chemistry of Hydrazinoalcohols and their Heterocyclic Derivatives. Part 1. Synthesis of Hydrazinoalcohols

“…Hydrolysis or acetolysis of N-phthaloylamino-substituted aziridines resulted in N 2 -phthaloyl-1,2-hydrazinoalcohol derivatives. The O-acetyl intermediates, formed by acetolysis, exhibited O → N acyl migration [188,189].…”

The Chemistry of Vicinal Diamines

“…[116] Thus, the opening of Nphthalimido-aziridines 233 by aniline, [117] and the ytterbium triflate catalyzed opening of N-protected aziridines 236 by amines [118] have been reported. Imidazole was recently shown to add to N-acylaziridines 238 under pressure, but modest yields of recovered products were obtained.…”

An Aldimine Cross‐Coupling for the Diastereoselective Synthesis of Unsymmetrical 1,2‐Diamines

“…[ Compared to other methods [28] that employ the attachment of amino groups to preexisting carbon frameworks such as alkenes, [29,30] aziridines, [31] epoxides, [32] and diols, [33] the selective aldimine cross-coupling has the advantage that a single regioisomer is formed independent of the substitution pattern of the reactants. The reaction sequence does not require protecting-group operations and can be performed in one pot.…”