Two methods were compared to convert ferrocene into N,N-diisopropylferrocenecarboxamide, N,N-diethylferrocenecarboxamide, N,N-dimethylferrocenecarboxamide, and (4-morpholinocarbonyl)ferrocene, namely, deprotometalation followed by trapping using dialkylcarbamoyl chlorides and amide formation from the intermediate carboxylic acid. The four ferrocenecarboxamides were functionalized at C²; in the case of the less hindered and more sensitive amides, recourse to a mixed lithium–zinc 2,2,6,6-tetramethylpiperidino-based base allowed us to achieve the reactions. Halogen migration using lithium amides was next optimized. Whereas it appeared impossible to isolate the less hindered 3-iodoferrocenecarboxamides, 3-iodo-N,N-diisopropylferrocenecarboxamide proved stable and was converted to new 1,3-disubstituted ferrocenes by Suzuki coupling or amide reduction. DFT calculations were used to rationalize the results obtained.

中文翻译：

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从2到3取代的二茂铁羧酰胺或如何在二茂铁系列中应用卤素“舞蹈”

两种方法进行比较，以转换成二茂铁Ñ，Ñ -diisopropylferrocenecarboxamide，Ñ，Ñ -diethylferrocenecarboxamide，Ñ，Ñ -dimethylferrocenecarboxamide，和（4-吗啉代）二茂铁，即deprotometalation随后从中间羧酸捕集使用二烷基氨基甲氯化物和酰胺形成酸。四种二茂铁羧酰胺在C ²官能化; 在酰胺受阻较少且较敏感的情况下，采用基于混合的锂锌2、2、6、6-四甲基哌啶子基的碱，可以实现反应。接下来优化了使用酰胺化锂的卤素迁移。尽管似乎不可能分离受阻较少的3-碘二茂铁羧酰胺，但是3-碘-N，N-二异丙基二茂铁羧酰胺被证明是稳定的，并通过Suzuki偶联或酰胺还原转化为新的1,3-二取代的二茂铁。DFT计算用于合理化获得的结果。