Intermolecular hydroaminoalkylation reactions of propadiene with selected secondary amines take place in the presence of a2 ,6-bis(phenylamino)pyridinato titanium catalyst. The corresponding products, synthetically useful allylamines, are formed in convincing yields and with high selectivities. In addition, propadiene easily inserts into the titanium-carbon bond of at itanaaziridine.
Organonickel(II)‐Komplexe des Typs [NiX{C6H3(CH2NR1R2)2‐2,6}] (X = Halogen, OH2+/CF3SO3−; R1R2Et 1; R1R2iPr 2; R1 = Me, R2 = Cy 3; (NR1R2) = piperidino 4; (NR1R2) = pyrrolidino 5) werden beschrieben. Die Charakterisierung erfolgte mit Hilfe der 1H und 13C‐NMR‐ sowie der UV/Vis‐Spektroskopie. Von 1 a (X = Br) wurde die Kristallstruktur bestimmt. Dieser Komplex kristallisiert orthorhombisch in der Raumgruppe Pbca mit a = 1 335,8(2) pm, b = 1 903,3(3) pm, c = 1 365,4(3) pm und Z = 8, er besitzt eine annähernd quadratisch‐planare Geometrie. 4 und 5 vermögen SO2 reversibel zu fixieren, was durch die IR‐Photoakustik‐Spektroskopie nachweisbar ist. Die Reaktionen von 1–5 mit CS2 und PhNSO werden diskutiert.
Intermolecular hydroaminoalkylation reactions of 1,1-and 1,3disubstituted allenes as well as methylenecyclopropanes with secondary amines can be achieved in the presence of a 2,6bis(phenylamino)pyridinato titanium catalyst at 140 °C within 2-8 h. Corresponding reactions of allenes with N-benzylanilines deliver branched allylamine products in very good yields (up to 83 %) and with branched-linear-ratios between 75 : 25 and 95 : 5.In contrast, bicyclic methylenecyclopropanes undergo hydroaminoalkylation with N-benzylanilines or N-alkylbenzylamines to give linear products in good to excellent yields (up to 98 %) with perfect regio-and diastereoselectivity. The corresponding 1,2,3-trisubstituted (2-aminoethyl)cyclopropane products exhibit a structurally interesting cis-orientation of all three cyclopropane hydrogen atoms.
Synthese und Eigenschaften von Sulfinato‐Nickel(II)‐Komplexen des Typs L2Ni(Cl)SO2R (L2 = TMED, bipy, phen, DPPE, (PBu3)2; R = Ph, p‐Tol, Me, NMe2) werden beschrieben. Die Charakterisierung der dargestellten Verbindungen erfolgte mit Hilfe magnetischer Messungen sowie der IR‐und Reflexionsspektroskopie.
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