Lewis acid mediated addition of 2-acyl-1,3-dithianes to α,β-unsaturated ketones: Synthesis of cyclohexenedione mono-dithioacetals.

Page, Philip C. Bulman; Marchington, Allan P.; Graham, Lisa J.; Harkin, Shaun A.; Wood, W. W.

doi:10.1016/s0040-4020(01)80563-9

Cited by 12 publications

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“…Despite the undisputable importance of 2-lithio-1,3-dithianes in synthetic chemistry, inconsistent yields and formation of side products have been reported . Problems derived from its high reactivity and strong basicity have been overcome either by transmetalation, − or using less reactive silyl, − or tin , analogues. The autoxidation of 2-lithio-1,3-dithiane (Scheme ) upon air exposure has been reported by Wade and co-workers, after observing formation of 1 and 2 in absence of an electrophile.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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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.

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