Department of Pharmaceutical and Biological Engineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, China.
Org Biomol Chem. 2019 Feb 20;17(8):2126-2133. doi: 10.1039/c8ob03019g.
A novel efficient metal-free aminoiodination of alkenes with N-fluorobenzenesulfonimide (NFSI) through an iodonium intermediate under mild conditions with good regioselectivity and stereoselectivity is reported. Unlike transition-metal catalysed aminative bisfunctionalization with NFSI in which the oxidative addition of NFSI to transition-metals affords an electrophilic amino radical, the oxidation of anionic iodide by NFSI in situ generates an electrophilic iodine cation and an amino nucleophile to fulfil this efficient reaction. 2,2,6,6-Tetramethyl-piperidine-1-oxyl (TEMPO) could considerably promote this iodoamination at room temperature. A preliminary trial suggests that bromoamination could also be achieved under similar conditions.
本文报道了一种在温和条件下，通过碘鎓中间体，以 N-氟代苯磺酰胺（NFSI）为高效无金属试剂对烯烃进行氨基碘代反应的方法。该方法具有良好的区域选择性和立体选择性。与 NFSI 催化的过渡金属参与的氨基双官能化反应不同，该反应中 NFSI 对过渡金属的加成反应生成亲电氨基自由基，而 NFSI 原位氧化阴离子碘化物生成亲电碘阳离子和氨基亲核试剂，从而实现了这一高效反应。2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）可以在室温下显著促进这种碘胺化反应。初步试验表明，类似条件下也可以实现溴胺化反应。
