Radical Benzylation of Quinones via C-H Abstraction.

Herein we report the development of radical benzylation reactions of quinones using Selectfluor and catalytic Ag(I) initiators. The reaction is believed to proceed via a C-H abstraction mechanism after Ag(I)-mediated reduction of Selectfluor. This reaction occurs under mild conditions and is effective for a variety of quinones and radical precursors bearing primary benzylic carbons. The use of preformed Ag(4-OMePy)2NO3 as a catalyst proved effective in improving the reaction efficiency by reducing unwanted degradation pathways available to Selectfluor.

Silver-Catalyzed Minisci Reactions Using Selectfluor as a Mild Oxidant.

A new method for silver-catalyzed Minisci reactions using Selectfluor as a mild oxidant is reported. Heteroarenes and quinones both participate in radical C-H alkylation and arylation from a variety of carboxylic and boronic acid radical precursors. Several oxidatively sensitive and highly reactive radical species are successful, providing structures that are challenging to access by other means.

Radical C-H Fluorination Using Unprotected Amino Acids as Radical Precursors.

We report a unique example of utilizing unprotected amino acids for benzylic C-H fluorination via a radical process. α-Aminoalkyl radicals are readily generated via oxidative decarboxylation of unprotected amino acids using a simple silver(I) catalyst and Selectfluor, which serves as both a mild oxidant and source of electrophilic fluorine. Mechanistic investigation shows that coordination of the unprotected amino acid plays a crucial role in lowering the oxidation potential of Ag(I), enabling oxidation under mild conditions. Mono- or difluorination is possible by controlling the stoichiometry of amino acid and fluorine source.

Unprotected Amino Acids as Stable Radical Precursors for Heterocycle C-H Functionalization.

An efficient and general method for the C-H alkylation of heteroarenes using unprotected amino acids as stable alkyl radical precursors is reported. This one-pot procedure is performed open to air under aqueous conditions and is effective for several natural and unnatural amino acids. Heterocycles of varying structure are suitably functionalized, and reactivity trends reflect the nucleophilic character of the radical species generated.

Enantioconvergent synthesis of (+)-aphanorphine via asymmetric Pd-catalyzed alkene carboamination.

A concise asymmetric synthesis of (+)-aphanorphine has been achieved via a new enantioconvergent strategy. A racemic γ-aminoalkene derivative is transformed into a 1:1 mixture of enantiomerically enriched diastereomers using an asymmetric Pd-catalyzed carboamination. This mixture is then converted to an enantiomerically enriched protected aphanorphine derivative by a Friedel-Crafts reaction, which generates a quaternary all-carbon stereocenter. The natural product is obtained in three additional steps.

Asymmetric palladium-catalyzed carboamination reactions for the synthesis of enantiomerically enriched 2-(arylmethyl)- and 2-(alkenylmethyl)pyrrolidines.

The enantioselective synthesis of 2-(arylmethyl)- and 2-(alkenylmethyl)pyrrolidine derivatives via Pd-catalyzed alkene carboamination reactions is described. These transformations generate enantiomerically enriched products with up to 94% ee from readily available alkenyl or aryl bromides and N-boc-pent-4-enylamines. The application of this method to a concise asymmetric synthesis of (-)-tylophorine is also discussed.

Numerical solution of differential equations using multiquadric radial basis functions networks.

This paper presents mesh-free procedures for solving linear differential equations (ODEs and elliptic PDEs) based on multiquadric (MQ) radial basis function networks (RBFNs). Based on our study of approximation of function and its derivatives using RBFNs that was reported in an earlier paper (Mai-Duy, N. & Tran-Cong, T. (1999). Approximation of function and its derivatives using radial basis function networks. Neural networks, submitted), new RBFN approximation procedures are developed in this paper for solving DEs, which can also be classified into two types: a direct (DRBFN) and an indirect (IRBFN) RBFN procedure. In the present procedures, the width of the RBFs is the only adjustable parameter according to a(i) = betad(i), where d(i) is the distance from the ith centre to the nearest centre. The IRBFN method is more accurate than the DRBFN one and experience so far shows that beta can be chosen in the range 7 < or = beta 10 for the former. Different combinations of RBF centres and collocation points (uniformly and randomly distributed) are tested on both regularly and irregularly shaped domains. The results for a 1D Poisson's equation show that the DRBFN and the IRBFN procedures achieve a norm of error of at least O(1.0 x 10(-4)) and O(1.0 x 10(-8)), respectively, with a centre density of 50. Similarly, the results for a 2D Poisson's equation show that the DRBFN and the IRBFN procedures achieve a norm of error of at least O(1.0 x 10(-3)) and O(1.0 x10(-6)) respectively, with a centre density of 12 X 12.