Ferrocenyl triflate (1) and 1,1′‐ferrocenediyl ditriflate (5) undergo single and double anionic thia‐Fries rearrangements at low temperatures in high yields with the latter forming exclusively the respective meso product. The detailed mechanisms of the anionic thia‐Fries rearrangement of 1, as well as that of the double anionic thia‐Fries rearrangement of 5, are examined with the aid of DFT calculations. Functionals, basis set and pseudopotentials applied were selected in accordance with a benchmark using the crystal structure analysis of the prime product 3 of the reaction of 1 before hydrolysis for comparison, which has so far not been reported. The unprecedented meso diastereoselectivity of the double anionic thia‐Fries rearrangement of 5 is shown to be a result of a distinctive degree of chelation arising from two diastereomeric transition states.

中文翻译：

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二茂铁上的阴离子硫代-弗里斯重排：计算和实验研究

三叶酸二茂铁基铁（1）和1,1'-二茂铁基二茂铁基（5）在低温下经历单和双阴离子硫代-弗里斯重排，后者仅形成各自的内消旋产物。阴离子硫杂的详细机制的Fries重排1，以及该双阴离子硫杂的弗里斯重排的5，与DFT计算的辅助被检查。使用1的反应的主要产物3的晶体结构分析，根据基准选择所应用的官能团，基集和拟电位水解之前进行比较，迄今为止尚未见报道。双阴离子硫杂-弗里斯重排5的空前介观非对映选择性表明，这是由于两个非对映异构过渡态引起的独特螯合度的结果。