6533b86efe1ef96bd12cc9f7
RESEARCH PRODUCT
Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes
Kari RissanenJoão R. ValeJoão R. ValeTatu RimpiläinenCarlos A. M. AfonsoNuno R. CandeiasElina I. Sievänensubject
116 Chemical sciencesorganometalliyhdisteet010402 general chemistryThioester01 natural sciencesMedicinal chemistryBenzaldehydechemistry.chemical_compoundorganometallic compoundsMoleculeta116chemistry.chemical_classificationAutoxidation010405 organic chemistryoxidation (passive)ArylOrganic ChemistryCondensationhapettuminenautooxidative condensation0104 chemical scienceslitiumchemistrylithiumYield (chemistry)Electrophiledescription
The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48-97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation with two other molecules of 2-aryl-2-lithio-1,3-dithiane. publishedVersion Peer reviewed
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2018-01-01 | The Journal of Organic Chemistry |