Regio- and Diastereoselective Synthesis of 2-Arylazetidines: Quantum Chemical Explanation of Baldwin’s Rules for the Ring-Formation Reactions of Oxiranes

Abstract

A general, scalable two-step regio- and diastereoselective method has been described for the synthesis of versatile alkaloid-type azetidines from simple building blocks with excellent overall yields. In the kinetically controlled reaction, only the formation of the strained four-membered ring can be achieved instead of the thermodynamically favorable five-membered rings under appropriate conditions. Remarkable functional group tolerance has also been demonstrated. In this paper, we give a new scope of Baldwin’s rules by density functional theory (DFT) calculations with an explicit solvent model, confirming the proposed reaction mechanisms and the role of kinetic controls in the stereochemical outcome of the reported transition-metal-free carbon–carbon bond formation reactions.

Synthesis and Fluorescence Mechanism of the Aminoimidazolone Analogues of the Green Fluorescent Protein: Towards Advanced Dyes with Enhanced Stokes Shift, Quantum Yield and Two‐Photon Absorption

“…Computation was carried out at M06‐2X/6‐31++G(d,p) level of theory, using integral equation formalism‐polarisable continuum model (IEFPCM) method with the parameters of methanol [68] . The method and basis sets were chosen for their reliability shown in earlier studies [69–71] . The vibrational frequencies were computed at the same levels of theory, as used for geometry optimisation, in order to properly confirm that all structures reside at minima on their potential energy hypersurfaces (PESs).…”

Actualización de las Reglas de Baldwin

“…Para esta síntesis se utiliza un método regio-y diasteroselectivo para las azetidinas de tipo alcaloide a partir de componentes básicos con buenos rendimientos. Para esto se diseñó un método a partir de las reglas de Baldwin, enriqueciendo la biblioteca química con una trans-3-(hidroximetil)-2-arilazetidinas, siendo de gran utilidad para el descubrimiento de fármacos a partir de bencilaminas sustituidas con oxiranilmetilo (Esquema 9) (Kovács et al, 2020).…”

Optical Study of Solvatochromic Isocyanoaminoanthracene Dyes and 1,5-Diaminoanthracene

“…To obtain an explanation for the spectral changes which take into account the electronic structure of the species, a previously tested calculation protocol was adopted [41][42][43]. The geometry optimization of solvated molecules (DAA-DIA) was carried out by using M06 [44] density functional combined with triple-ζ Karlsruhe basis set (TZVP) [45].…”