Ac yclic (alkyl)(amino)carbene (CAAC) has been shown to react with acovalentazide similar to the Staudinger reaction. The reaction of Me CAAC with trimethylsilyl azide afforded the N-silylated 2-iminopyrrolidine ( Me CAAC=NSiMe 3 ), which was fully characterized. This compound undergoes hydrolysis to afford the 2-iminopyrrolidine and trimethylsiloxane which co-crystallize as ah ydrogen-bonded adduct. The N-silylated 2-iminopyrrolidine was used to transfer the novel pyrrolidine-2-iminatol igand onto both main-group and transition-metal centers. The reactiono ft he tetrabromodiborane bis(dimethyl sulfide) adduct with two equivalents of Me CAAC=NSiMe 3 afforded the disubstituted diborane.
Heterocycles containing group 13 and 15 elements such as borazines are an integral part of organic, biomedical and materials chemistry. Surprisingly, heterocycles containing P and Al are rare. We have now utilized phosphaalumenes in reactions with alkynes, alkenes and conjugated double bond systems. With sterically demanding alkynes 1,2‐phosphaalumetes were afforded, whereas the reaction with HCCH or HCCSiMe3 gave 1,4‐phosphaaluminabarrelenes. Using styrene saturated 1,2‐phosphaalumates were formed, which reacted further with additional styrene to give different regio‐isomers of 1,4‐aluminaphosphorinanes. Using ethylene, a 1,4‐aluminaphosphorinane is obtained, while with 1,3‐butadiene a bicyclic system containing an aluminacyclopentane and a phosphirane unit was synthesized. The experimental work is supported by theoretical studies to shed light on the mechanism governing the formation of these heterocycles.
Carbon dioxide is an intrinsically stable molecule; however, it can readily react with various nucleophilic reagents. In the presence of a cyanide source, CO2 was proven to be useful to promote addition reactions. Here we report the use of CO2 to facilitate 1,4-conjugate cyanide addition reaction to chalcones to generate organonitriles. Nitriles are key component in organic synthesis due to their utility in numerous functional group transformation, however, conjugation addition of cyanide has been a challenge in this substrate class due to side reactions. To mitigate this, we employed simple ammonium and metal cyanide sources as nucleophiles under carbon dioxide atmosphere where high selectivity toward the desired product was obtained. The presented reaction is not feasible under inert atmosphere, which highlights the important role of CO2, as a Lewis and Brøndsted acidic catalyst. Further derivatization of organonitriles compounds were performed to showcase the utility of the reaction, while an unprecedented dimerization reaction was identified and characterized, affording a cyclopentanone scaffold.
Heterocyclen, die Elemente der Gruppen 13 und 15 enthalten, wie z. B. Borazine, sind ein fester Bestandteil der organischen, biomedizinischen und Materialchemie. Überraschenderweise sind Heterocyclen, die P und Al enthalten, selten. Wir haben nun Phosphaalumene in Reaktionen mit Alkinen, Alkenen und konjugierten Doppelbindungssystemen eingesetzt. Mit sterisch anspruchsvollen Alkinen wurden 1,2‐Phosphaalumete erhalten, während die Reaktion mit HCCH oder HCCSiMe3 1,4‐Phosphaaluminabarrelene ergab. Mit Styrol wurden gesättigte 1,2‐Phosphaalumate gebildet, die mit weiteren Äquivalenten Styrol zu verschiedenen Regio‐Isomeren von 1,4‐Aluminaphosphorinanen weiterreagierten. Mit Ethylen wird ebenfalls ein 1,4‐Aluminaphosphorinan erhalten, während mit 1,3‐Butadien ein bicyclisches System mit einer Aluminacyclopentan‐ und einer Phosphiran‐Einheit synthetisiert wurde. Die experimentellen Arbeiten werden durch theoretische Studien unterstützt, um den Mechanismus der Bildung dieser Heterocyclen genauer zu untersuchen.
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