Primary alkoxyl free radicals were generated from their readily synthesized N-phthalimido derivatives under reductive conditions. Primary alkoxyl radicals derived from their corresponding xylo- and ribofuranose derivatives underwent, exclusively, an unusual beta-fragmentation affording L-threose and D-erythrose derivatives, respectively. This occurs because the alkoxyl radical is capable of achieving an internal hydrogen-bonding interaction leading to a stable six-membered ring intramolecular hydrogen-bonded structure. When the hydroxyl group is protected, the beta-fragmentation pathway is prevented and the hydrogen atom transfer (HAT) pathway occurs. Computational studies provided strong support for the experimental observations.
By using cheap and innocuous reagents, such as NaClO 2 , NaOCl, and catalytic amounts of TEMPO, a new environmentally friendly protocol for the selective and catalytic TEMPO C(sp 3 )−H oxidation of piperazines and morpholines to 2,3-diketopiperazines (2,3-DKP) and 3morpholinones (3-MPs), respectively, has been developed. This novel direct access to 2,3-DKP from piperazines provides significant advantages over the traditional N-monoacylation/ intramolecular C−N cyclization procedure. Additionally, by modulating the amounts of TEMPO, 2-alkoxyamino-3morpholinone can be prepared from morpholine derivatives, which would enable further functionalization at the C2 position of the morpholine skeleton.
In this paper we describe a probabilistic framework for describing dynamical systems. The approach is inspired by quantum dynamical expectation dynamics. Specifically, an abstract evolution operator corresponding to the Hamiltonian in quantum dynamics is constructed. The evolution of this operator defining PDE's solution is isomorphic to the functional structure of the wave function as long as its initial form permits. This operator enables us to use one of the most important probabilistic concepts, namely expectations. The expectation dynamics are governed by equations which are constructed via commutator algebra. Based on inspiration from quantum dynamics, we have used both the independent variables and the symmetric forms of their derivatives. For construction of the expectation dynamics, the algebraic independent variable operators which multiply their operands by the corresponding independent variable suffice. In our descriptions, we remain at the conceptual level in a self-consistent manner. The phenomenological implications and the tremendous potential of this approach for scientific discovery and advancement is described in the companion to this paper. M. Demiralp (B)
Addition of organocuprates, generated in situ using an excess of a 1:2 mixture of CuI·DMS and Grignard reagent, to N-enoyl oxazolidinethiones in the presence of excess TMSI gave preferentially the anti diastereomer where the addition took place when the conformation of the substrate was syn-s-cis. The reaction was investigated with indene-based and three different phenyl glycine derived oxazolidinethiones.
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