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Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes.

ABSTRACT: 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 ?-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and ?-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.

SUBMITTER: Vale JR

PROVIDER: S-EPMC6150673 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature

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Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes.

Vale João R JR Rimpiläinen Tatu T Sievänen Elina E Rissanen Kari K Afonso Carlos A M CAM Candeias Nuno R NR

The Journal of organic chemistry 20180126 4

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 ...[more]

PMID: 29334462

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