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Photocatalytic Stoichiometric Oxidant-Free Synthesis of Linear Unsaturated Ketones from 1,2-Disubstituted Cyclopropanols
Synthesis ( IF 2.2 ) Pub Date : 2020-12-01 , DOI: 10.1055/s-0040-1706088
Alaksiej L. Hurski , Marharyta V. Laktsevich-Iskryk , Anastasiya V. Krech , Vladimir N. Zhabinskii , Vladimir A. Khripach

A one-step catalytic oxidant-free synthesis of unsaturated ketones from 1,2-disubstituted cyclopropanols is reported. Previously for this transformation, only two- and three-step protocols have been developed. The reaction proceeds under irradiation with visible light in the presence of catalytic amounts of both an acridinium photocatalyst and a cobaloxime complex. 2-Aryl-substituted cyclopropanols react giving α,β-unsaturated ketones, while dehydrogenative ring opening of 2-alkyl-substituted substrates affords mixtures of α,β- and β,γ-enones. The reaction starts with one-electron oxidation of a cyclopropanol to cyclopropyloxy radical, presumably, by the photoexcited acridinium catalyst. We also found that Co(dmgBF2)2(MeCN)2 complex under an air atmosphere and irradiation with blue LEDs or upon heating can serve as a hydroxycyclopropane oxidant.



中文翻译:

由1,2-二取代的环丙醇光催化合成无氧化剂的线性不饱和酮

据报道,由1,2-二取代的环丙醇可一步催化无氧化剂合成不饱和酮。以前,此转换仅开发了两步和三步协议。该反应在催化量的photo啶光催化剂和钴肟肟络合物的存在下在可见光的照射下进行。2-芳基取代的环丙醇反应生成α,β-不饱和酮,而2-烷基取代的底物的脱氢开环提供α,β-和β,γ-烯酮的混合物。该反应开始于环丙醇被光激发的to啶催化剂单电子氧化为环丙氧基。我们还发现Co(dmgBF 22(MeCN)2 在空气气氛下用蓝色LED照射或加热时生成的配合物可用作羟基环丙烷氧化剂。

更新日期:2020-12-02
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