Decarboxylative Bromination of Sterically Hindered Carboxylic Acids with Hypervalent Iodine(III) Reagents
Decarboxylative Bromination of Sterically Hindered Carboxylic Acids with Hypervalent Iodine(III) Reagents
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DOI：
10.1021/acs.oprd.0c00130
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发表时间：
2020-06
影响因子：
3.4
通讯作者：
Ayumi Watanabe;Kenta Koyamada;K. Miyamoto;Junichiro Kanazawa;M. Uchiyama
中科院分区：
文献类型：
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作者：
Ayumi Watanabe;Kenta Koyamada;K. Miyamoto;Junichiro Kanazawa;M. Uchiyama
空间受阻的三维卤代烷基化合物是一种很有希望用于各种反应的前驱体，但它们很难通过传统的反应合成。我们提出了一种有效和实用的方法，使用商业上可获得的(二乙氧基碘)苯和溴化钾，对空间受阻的3D脂肪族羧酸进行脱羧基溴化反应，这是自然界最稳定和最便宜的溴源之一。该方法具有无金属/无Br2体系、反应条件温和、常温空气下一锅操作、广泛的官能团相容性和克级合成能力等特点。这种高效的反应干净地将广泛的羧酸转化为相应的烷基溴化物，产率从好到高。羧酸是高度紧张/自然发生/与药物相关的支架的最便宜和最容易获得的来源。
Sterically hindered three-dimensional (3D) alkyl halides are promising precursors for various reactions; however, they are difficult to synthesize via conventional reactions. We present an efficient and practical method for decarboxylative bromination of sterically hindered 3D aliphatic carboxylic acids using commercially available (diacetoxyiodo)benzene and potassium bromide, one of the most stable and cheapest bromine sources in nature. The present method features a metal-free/Br2-free system, mild reaction conditions, one-pot operation under air at room temperature, wide functional group compatibility, and gram-scale synthetic capability. This highly efficient reaction cleanly converts a broad range of carboxylic acids, the most inexpensive and readily available sources of highly strained/naturally occurring/drug-related scaffolds, into the corresponding alkyl bromides in good to high yields.