Selective Catalytic Oxidation of Alcohols, Aldehydes, Alkanes and Alkenes Employing Manganese Catalysts and Hydrogen Peroxide
Selective Catalytic Oxidation of Alcohols, Aldehydes, Alkanes and Alkenes Employing Manganese Catalysts and Hydrogen Peroxide
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DOI：
10.1002/adsc.201300275
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发表时间：
2013-09
影响因子：
5.4
通讯作者：
Pattama Saisaha;L. Buettner;M. V. D. Meer;R. Hage;B. Feringa;W. Browne;J. W. D. Boer
中科院分区：
文献类型：
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作者：
Pattama Saisaha;L. Buettner;M. V. D. Meer;R. Hage;B. Feringa;W. Browne;J. W. D. Boer
含锰催化体系[（Mn_2 O_3）-O-IV，IV（tmtacn）（2）]（2+）（1）/羧酸（其中tmtacn=N，N，N-三甲基-1，4，7-三氮杂环壬烷）最初被鉴定用于烯烃的顺式-二羟基化和环氧化反应，现已被广泛应用于各种氧化转化反应，包括以H_2 O_2为氧化剂的烷烃、醇和醛的氧化。检查的底物类包括伯和仲脂肪族和芳香族醇，醛和烯烃。重点不是主要确定每个单独的基板的最佳条件，但理解的各种因素，影响的Mn-tmtacn催化系统的反应性，并探讨哪些官能团被优先氧化。该催化体系以高原子效率的方式使用H2 O2，其反应性可以通过改变原位形成的[Mn-2（III，III）（O）（RCO 2）（2）（tmtacn）（2）]（2+）二聚体的羧基配体来调节。此外，含有一个以上氧化敏感基团的几种底物可以被选择性氧化，在某些情况下，甚至在没有保护基团的情况下。
The manganese-containing catalytic system [(Mn2O3)-O-IV,IV(tmtacn)(2)](2+) (1)/carboxylic acid (where tmtacn=N,N,N-trimethyl-1,4,7-triazacyclononane), initially identified for the cis-dihydroxylation and epoxidation of alkenes, is applied for a wide range of oxidative transformations, including oxidation of alkanes, alcohols and aldehydes employing H2O2 as oxidant. The substrate classes examined include primary and secondary aliphatic and aromatic alcohols, aldehydes, and alkenes. The emphasis is not primarily on identifying optimum conditions for each individual substrate, but understanding the various factors that affect the reactivity of the Mn-tmtacn catalytic system and to explore which functional groups are oxidised preferentially. This catalytic system, of which the reactivity can be tuned by variation of the carboxylato ligands of the in situ formed [Mn-2(III,III)(O)(RCO2)(2)(tmtacn)(2)](2+) dimers, employs H2O2 in a highly atom efficient manner. In addition, several substrates containing more than one oxidation sensitive group could be oxidised selectively, in certain cases even in the absence of protecting groups.