Über Umsetzungen von Iminiumsalzen mit Arylmagnesiumhalogeniden

Abstract

Arylmagnesiumhalogenide werden an Iminiumsalze 1 -6,' die von Pyrrolidin und Aldehyden oder cyclischen Ketonen abgeleitet sind, nucleophil unter Bildung der tertiaren Amine 7 -21 addiert. Die Umsetzung von N, N-Dimethyl(diphenylen)ammoniumjodid (23) und Arylmagnesiumhalogeniden fuhrt unter Hydridubertragung zu N, N-Dimethyl(dipheny1methyl)amin (22); daneben entsteht durch Deprotonierung einer Methylgruppe am Iminiumstickstoff N, N, "-Trimethyl-1,l-diphenylathandiamin (25). Reactions of lminium Salts with Arylmagnesium HalidesThe tertiary amines 7 -21 are formed from iminium salts 1 -6 which are derived from pyrrolidine and aldehydes or cyclic ketones, by nucleophilic attack of arylmagnesium halides. Upon arylmagnesium halide addition to N, N-dimethyl(diphenylmethy1ene)ammonium iodide (23) hydride transfer takes place to give N, N-dimethyl(diphenylmethy1)amine (22). Furthermore, deprotonation of a methyl group attacked on iminium nitrogen affords N,N, N'-trimethyl-1,l-diphenylethanediamine (25). Umsetzungen von Iminiumsalzen mit Grignard-Reagenzien wurden bisher bevorzugt mit Alkylmagnesiumhalogeniden durchgefuhrt und lieferten die durch nucleophileAddition am Iminiumkohlenstoff entstehenden tertiaren Amine I). Eine sorgfaltige Untersuchung des aus 4-tert-Butylcyclohexanon und Dimethylammoniumperchlorat dargestellten Iminiumsalzes lehrte jedoch, da8 bei dessen Umsetzung mit Isopropyl-, sec-oder tert-Butyl-sowie Cyclohexylmagnesiumchlorid Addition und Hydridubertragung nebeneinander ablaufen". Auch Aryl-und Diarylmethylenammoniumsalze Vgl.

Preparation and analytical characterization of 1‐(1‐phenylcyclohexyl)piperidine (PCP) and 1‐(1‐phenylcyclohexyl)pyrrolidine (PCPy) analogues

“…[12,[18][19][20] Data for the PCPy series is less available, with only a single publication describing the synthesis of 4-MeO-PCPy (5b) from the iminium salt. [21] To the best of the authors' knowledge it would also appear that 3-MeO-PCPy (5a) and 3-Me-PCPy (5c) have not yet been described in the scientific literature and information on the potential to be psychoactive in humans is absent. Although preparations of some of these substances have been described in some of the earlier medicinal and organic chemistry literature, less is known about their analytical features which are especially important for clinical and forensic purposes.…”

Nucleophilic Aminoalkylation. Lithiated N,N‐Dimethylthiopivalamide

“…95.5"C). Neopentylamines are accessible from ( 5 ) by desulfuration with LiA1H4[4b.101 (example: (7); 88 %; m.p. 84.5"C).…”

Regio- and chemoselective Csp3–H arylation of benzylamines by single electron transfer/hydrogen atom transfer synergistic catalysis

“…Nucleophilic addition of an aryl nucleophile to an imine or an iminium ion is a commonly used strategy to construct the 1,1-diarylmethylamine core. 4 On the other hand, recent work has explored direct benzylic Csp 3 –H arylation of amine derivatives ( Scheme 1 ). Li and co-workers reported an oxidative cross-dehydrogenative coupling reaction of N -aryl tetrahydroisoquinolines (THIQs) via in situ oxidation to iminium ions ( Scheme 1A ).…”