Rabong, C. V. (2007). Scope and limitations of the t-reaction with emphasis on the synthesis of chiral heterocycles. [Diploma Thesis, Technische Universität Wien]. reposiTUm. http://hdl.handle.net/20.500.12708/181924
Employing a two-step sequence consisting of 1) nucleophilic aromatic substitution of ortho-Halo (Halogen=F, Cl) aromatic aldehydes or 1.1) Pd-catalyzed Buchwald-Hartwig aryl amination of ortho-Halo (Halo=Cl, Br) aromatic aldehydes with mostly (bi)cyclic secondary amines followed by 2) ring-closure via tert. amino effect (a sigmatropic [1,5]-hydride-shift) with C-H-acidic active methylene compounds as the key step, we obtained new heterocycles in mostly excellent yield and purity.<br />Further, we examined the stereoselectivity of the transformation in cases where it was deemed significant by means of single-crystal-X-Ray-diffraction (XRD) and correlated nuclear magnetic resonance spectroscopy (1H-1H- and 1H-13C - COSY-NMR); we used quantum mechanical calculations to support our reasoning, aswell.
