1,3-Diamine Formation from an Interrupted Hofmann–Löffler Reaction: Iodine Catalyst Turnover through Ritter-Type Amination

An
iodine-catalyzed Ritter-type amination of nonactivated C–H
bonds is presented enabling the formation of 1,3-α-tertiary
diamines. A sulfamidyl radical serves as the promoter in a guided
tertiary C–H iodination through an exclusive 1,6-HAT process.
The subsequent Ritter reaction furnishes the C–N bond and establishes
an unprecedented concept for catalyst turnover in iodine redox catalysis.
The general robustness of the methodology, including broad functional
group tolerance, was demonstrated for 24 different 1,3-diamine derivatives,
which were synthesized in yields of 42%–99%.

本研究报道了一种可实现非活化C–H键碘催化Ritter型胺化反应的方法，能够合成1,3-α-叔二胺类化合物。该过程以磺酰胺基自由基作为促进剂，通过专一性的1,6-氢原子转移（1,6-HAT）介导叔C–H键的碘化反应。后续的Ritter反应构建了C–N键，同时为碘氧化还原催化体系中的催化剂周转建立了前所未有的新思路。本研究针对24种不同的1,3-二胺衍生物验证了该方法的普适性，包括其优异的官能团耐受性，目标产物产率介于42%~99%之间。