Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst.
Oxidative Cleavage of Alkenes by O(2) with a Non-Heme Manganese Catalyst.
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DOI：
10.1021/jacs.1c05757
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发表时间：
2021-07-07
影响因子：
15
通讯作者：
Xiao J
中科院分区：
文献类型：
--
作者：
Huang Z;Guan R;Shanmugam M;Bennett EL;Robertson CM;Brookfield A;McInnes EJL;Xiao J
C=C双键与分子氧氧化裂解生成羰基化合物是化学和药物合成中的一个重要转化。在自然界中，含有第一排过渡金属的酶，特别是血红素和非血红素铁依赖性酶，在环境条件下很容易激活O2并以极高的精度氧化切割C=C键。然而，对合成化学家来说，这种反应仍然具有挑战性。只有少数已知的合成金属催化剂能在O2大气压下催化烯烃的氧化裂解，而很少有已知的催化剂能催化非活化烯烃的裂解。在这项工作中，我们描述了一种光驱动，锰催化的方案，用于在1atm O2下选择性氧化烯烃为羰基。首次在清洁、温和的条件下，在第一排生物相关金属催化剂的催化下，芳香族和各种非活化的脂肪族烯烃被氧化生成酮类和醛类。此外，该方案具有很好的功能群容忍度。机理研究表明，不对称的混价双（μ-氧）-Mn（III，IV）配合物参与了氧化反应，溶剂甲醇参与O2活化，形成氧。
The oxidative cleavage of C=C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C=C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn–oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
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影响因子：
4.6
作者：
Colmer, Hannah E.;Howcroft, Anthony W.;Jackson, Timothy A.
通讯作者：
Jackson, Timothy A.
影响因子：
0.8
作者：
Koike, K;Inoue, G;Fukuda, T
通讯作者：
Fukuda, T
影响因子：
3.4
作者：
Hida, Takemasa;Kikuchi, Junko;Nogusa, Hideo
通讯作者：
Nogusa, Hideo
通过系统的配体修饰来调整锰二氧化物和过氧中间体的相对稳定性和反应性。
影响因子：
18.3
作者：
Kovacs JA
通讯作者：
Kovacs JA
影响因子：
15
作者：
Gonzalez-de-Castro, Angela;Xiao, Jianliang
通讯作者：
Xiao, Jianliang