α‐Amination of Carbonyl Compounds by Using Hypervalent Iodine‐Based Aminating Reagents Containing a Transferable (Diarylmethylene)amino Group
α‐Amination of Carbonyl Compounds by Using Hypervalent Iodine‐Based Aminating Reagents Containing a Transferable (Diarylmethylene)amino Group
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使用含有可转移（二芳基亚甲基）氨基的高价碘基胺化试剂对羰基化合物进行 α-胺化
DOI：
10.1002/chem.202203722
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发表时间：
2023
影响因子：
4.3
通讯作者：
Minakata Satoshi
中科院分区：
文献类型：
--
作者：
Okumatsu Daichi;Kawanaka Kazuki;Kainuma Shunpei;Kiyokawa Kensuke;Minakata Satoshi
含有可转移（二芳基亚甲基）氨基的高价碘基胺化试剂可用于在锂碱存在下对简单羰基化合物（如酯、酰胺和酮）进行α-胺化。产物的（二芳基亚甲基）氨基可以容易地改性，从而提供获得伯胺和二芳基甲胺的途径。所开发的方法具有不含过渡金属的条件和简单的一锅法程序，而无需单独制备烯醇化物等价物，从而为合成各种α-氨基羰基化合物提供了通用和实用的方法。实验机理研究表明，这种胺化通过α-羰基与亚胺基的独特自由基偶联进行;它们通过烯醇化锂和高价碘试剂之间的单电子转移产生。
Hypervalent iodine‐based aminating reagents containing a transferable (diarylmethylene)amino group can be used for the α‐amination of simple carbonyl compounds such as esters, amides, and ketones in the presence of a lithium base. The (diarylmethylene)amino groups of the products can be readily modified, thus providing access to primary amines and diarylmethylamines. The developed method features transition‐metal‐free conditions and a simple one‐pot procedure without the need to prepare enolate equivalents separately, thus offering a general and practical approach to the synthesis of a wide variety of α‐amino carbonyl compounds. Experimental mechanistic investigations indicate that this amination proceeds through a unique radical coupling of an α‐carbonyl radical with an iminyl radical; they are generated through a single‐electron transfer between a lithium enolate and the hypervalent iodine reagent.