OXIDATION OF VICINAL DIOLS TO ALPHA-DICARBONYL COMPOUNDS BY TRIFLUOROACETIC-ANHYDRIDE ACTIVATED DIMETHYLSULFOXIDE
OXIDATION OF VICINAL DIOLS TO ALPHA-DICARBONYL COMPOUNDS BY TRIFLUOROACETIC-ANHYDRIDE ACTIVATED DIMETHYLSULFOXIDE
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DOI：
10.1021/jo00231a005
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发表时间：
1987-10-30
影响因子：
3.6
通讯作者：
GRAVATT, GL
中科院分区：
文献类型：
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作者：
AMON, CM;BANWELL, MG;GRAVATT, GL
三氟乙酸酐活化的二甲基亚砜是一种有效的氧化剂，可将邻位二醇转化为相应的二羰基化合物或衍生物。与Swern氧化剂不同，标题试剂系统给出了来自卤化底物的产物的良好产率。该方法允许合成以前无法获得的化合物，包括环戊酚酮、α-高邻-苯醌和“高反应性”-酮醛。在环戊酚酮新路线的开发方面，我们观察到2三氟乙酸酐（TFAA）/二甲基亚砜/三乙胺（Et 3 N）试剂系统3有效地（> 73%产率）转化各种7-卤代双环[4.1. 0]庚烷-2，3-和-3，4-二醇转化为相应的二酮。与此相反，使用其它氧化剂2，其中许多以前已用于将邻位二醇转化为-羟基酮4，5或-二酮，6 7 - 9，导致双环二醇的分解[与（Ph 3 P）3RuCl 2，苄叉丙酮，四氢呋喃（TH-F），195 ℃，10 h 8]，所需产物的产率低（<25（草酰氯，二甲亚砜，Et 3 N9），或不反应（N-氯琥珀酰亚胺，二甲硫醚，Et 3 N5; 4
Trifluoroacetic anhydride “activated” dimethyl sulfoxide is an effective oxidant for the conversion of vicinal diols into thecorresponding-dicarbonyl compounds or products derived therefrom. Unlike the Swern oxidant, the title reagent system gives good yields of products derived from halogenated substrates. The method has permitted syntheses of previouslyinaccessible compounds including tropolones, a-homo-o-benzoquinone, and a “hyperreactive”-keto aldehyde.In connection with the development of a new route to tropolones, we observed2 that the trifluoroacetic anhydride (TFAA)/dimethyl sulfoxide/triethylamine (Et3N) reagent system3 efficiently (> 73% yield) converts various 7-halo-bicyclo [4.1. 0] heptane-2, 3-and-3, 4-diols into the corre-sponding-diketones. In contrast, the use2 of otheroxidizing agents, many of which have been previously em-ployed for converting vicinal diols into-hydroxy ketones4, 5 or-diketones, 6 7" 9 led to decomposition of the bicyclic diols [with (Ph3P) 3RuCl2, benzalacetone, tetrahydrofuran (TH-F), 195 C, 10 h8], low yields (< 25%) of the desired products (oxalyl chloride, dimethyl sulfoxide, Et3N9), or no reaction (N-chlorosuccinimide, dimethyl sulfide, Et^ N 5; 4