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Intramolecular Homolytic Substitution of Sulfinates and Sulfinamides

机译:亚砜和亚磺酰胺的分子内均质取代

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摘要

A general and efficientmethod for the synthesis of cyclic sulfi-nates and sulfinamides based on intra-molecular homolytic substitution (SHi)at the sulfur atom by aryl or alkyl radi-cals is described. Both alkyl and benzo-fused compounds can be accessed di-rectly from easily prepared acyclic pre-cursors. Enantiomerically enriched sulfur-based heterocycles were formedthrough an SHi process with inversionof configuration at the sulfur atom.Cyclization of prochiral radicals pro-ceeded with varying stereochemicaloutcomes, depending on the size of theincoming radical. 2-Pyridyl and 2-qui-nolyl radicals led to biaryl compounds,which result from attack onto the orthoposition of the arylsulfinate rather thana thiophilic substitution.
机译:描述了基于芳基或烷基基团在硫原子上的分子内均质取代(SHi)的合成环状亚磺酸酯和亚磺酰胺的通用且有效的方法。烷基和苯并稠合的化合物都可以从容易制备的无环前体直接获得。对映体富集的硫基杂环是通过SHi过程形成的,在硫原子上的构型反转。前手性自由基的环化根据立体化学自由基的大小而变化。 2-吡啶基和2-喹啉基生成联芳基化合物,这是由于攻击芳基亚磺酸盐的原位而不是亲硫取代引起的。

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