UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France.
Chemistry. 2009 Oct 5;15(39):10225-32. doi: 10.1002/chem.200900942.
A general and efficient method for the synthesis of cyclic sulfinates and sulfinamides based on intramolecular homolytic substitution (S(H)i) at the sulfur atom by aryl or alkyl radicals is described. Both alkyl and benzofused compounds can be accessed directly from easily prepared acyclic precursors. Enantiomerically enriched sulfur-based heterocycles were formed through an S(H)i process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2-Pyridyl and 2-quinolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.
本文描述了一种通过芳基或烷基自由基在硫原子上发生分子内均裂取代（S(H)i）来合成环状亚砜和亚磺酰胺的通用、高效方法。通过简单制备的非环前体可以直接得到烷基和苯并稠合化合物。通过 S(H)i 过程形成对映体富集的含硫杂环，其中硫原子的构型发生反转。前手性自由基的环化反应具有不同的立体化学结果，具体取决于进入的自由基的大小。2-吡啶基和 2-喹啉基自由基导致联芳烃化合物的形成，这是由于芳基亚砜的邻位而不是亲硫取代发生攻击所致。
