Plöger Stefanie, Mück-Lichtenfeld Christian, Daniliuc Constantin G, Studer Armido
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster Corrensstraße 40 48149 Münster Germany
Chem Sci. 2022 Aug 5;13(33):9749-9754. doi: 10.1039/d2sc03860a. eCollection 2022 Aug 24.
An atom-economic thermal α,β-difunctionalization of various styrenes with readily prepared azodioxy compounds is reported. Mechanistic studies reveal that the starting azodioxy compounds can thermally be cleaved to the corresponding C-nitroso compounds, which under these thermal conditions further homolyze to generate reactive C-radicals along with the persistent NO radical. In the presence of a styrene, C-radical addition with subsequent nitrosylation followed by tautomerization is occurring, resulting in an overall styrene β-alkylation-α-oximation reaction.
报道了各种苯乙烯与易于制备的偶氮二氧基化合物的原子经济性热α,β-双官能化反应。机理研究表明，起始的偶氮二氧基化合物可热裂解为相应的亚硝基化合物，在这些热条件下，亚硝基化合物进一步均裂生成活性碳自由基和持久性的NO自由基。在苯乙烯存在下，发生碳自由基加成，随后进行亚硝基化，再经互变异构，从而得到整体的苯乙烯β-烷基化-α-肟化反应。
