An aerobic, organocatalytic, and chemoselective method for Baeyer-Villiger oxidation
An aerobic, organocatalytic, and chemoselective method for Baeyer-Villiger oxidation
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DOI：
10.1002/anie.200462429
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Naota, T
中科院分区：
文献类型：
--
作者：
Imada, Y;Iida, H;Naota, T
近年来，将分子氧直接掺入有机底物作为一种具有前瞻性的温和绿色分子转化技术而受到广泛关注一个非常紧迫的课题是发展有机催化方法这些方法应该促进新的策略，为使用氧化过渡金属配合物的传统不可持续工艺提供替代方案有限数量的有机催化有氧氧化已被报道。这些反应涉及到利用半稳定有机自由基[4]和光诱导电子转移系统从O2开始的多步自由基转移过程。最近，通过模拟微粒体含fad单加氧酶的酶促功能，提出了一种新的有机催化有氧氧化杂原子有机化合物的方法由于这个新系统包括将分子氧直接转化为合成的黄素氢过氧化物，而黄素氢过氧化物对各种有机底物都具有高活性[8,9]，因此该反应的原理应该能够实现具有高选择性和可控制性的可持续的有氧氧化化学。作为该系统的变体，我们在此描述了Baeyer-Villiger氧化的第一种有机催化有氧方法，该方法对这种亲核氧化表现出罕见的高化学选择性[Eq.(1)]。Baeyer-Villiger氧化是一类特殊的亲核氧化转化，它通过非催化的bbb和bbb与过氧化物和过酸进行
Direct incorporation of molecular oxygen into organic substrates has recently attained widespread interest as a forwardlooking technology for mild and green molecular transformations.[1] One subject of great urgency is the development of organocatalytic methods.[2] These methods should facilitate new strategies that provide an alternative to the conventional unsustainable processes, which use oxygenated transitionmetal complexes.[3] A limited number of organocatalytic aerobic oxidations has been reported. These reactions involve a multistep radical-transfer process from O2 by using semistable organic radicals [4] and photoinduced electron-transfer systems.[5]A new method for organocatalytic aerobic oxidation of heteroatomic organic compounds [6] was recently developed by simulating the enzymatic function of microsomal FAD-containing monooxygenase.[7] As this new system includes the direct conversion of molecular oxygen into synthetic flavin hydroperoxides, which are highly reactive towards various organic substrates,[8, 9] the principle of the reaction should enable sustainable aerobic oxidation chemistry with high selectivity and controllability. As a variation on this system, we describe herein the first organocatalytic aerobic method of the Baeyer–Villiger oxidation, which exhibits rare and high chemoselectivity for this nucleophilic oxidation [Eq.(1)]. The Baeyer–Villiger oxidation is a special class of nucleophilic oxidative transformation that proceeds specifically with peroxides and peracids through noncatalytic [10] and