Oxidative Cleavage of Cyanoketophosphoranes by Dimethyldioxirane

June 14, 2024

• Title:       

  Oxidative Cleavage of Cyanoketophosphoranes by Dimethyldioxirane

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  Synthesis of α-keto esters and amides via oxidative cleavage of cyanoketophosphoranes by dimethyldioxirane

• Mark:

  Table 1

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  α-Keto esters and amides were prepared by using two slightly different protocols. For the preparation of α-keto esters 1a -12a (Table 1, entries 1-12), dimethyldioxirane (CAS74087-85-7) (2 equiv, 0.04-0.06 M in acetone (CAS67-64-1)) was added to solutions of cyanoketophosphoranes 1-12 in MeOH (CAS 67-56-1). For the preparation of R-keto amides 13a and 14a (Table 1, entries 13 and 14), 1 equiv of the corresponding amine in CH₂Cl₂ (CAS 75-09-2) was added after the oxidative cleavage reaction was complete in CH₂Cl₂ at -78 °C as judged by TLC (within 5 min).