Pot-economy autooxidative condensation of 2-Aryl-2-lithio-1,3-dithianes

Joao R. Vale; Tatu Rimpiläinen; Elina Sievänen; Kari Rissanen; Carlos A.M. Afonso; Nuno R. Candeias

doi:10.1021/acs.joc.7b02896

Pot-economy autooxidative condensation of 2-Aryl-2-lithio-1,3-dithianes

Joao R. Vale, Tatu Rimpiläinen, Elina Sievänen, Kari Rissanen, Carlos A.M. Afonso, Nuno R. Candeias

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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 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.

Original language	English
Pages (from-to)	1948-1958
Number of pages	11
Journal	Journal of Organic Chemistry
Volume	83
Issue number	4
DOIs	https://doi.org/10.1021/acs.joc.7b02896
Publication status	Published - 16 Feb 2018
Publication type	A1 Journal article-refereed

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Organic Chemistry

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title = "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 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.",

author = "Vale, {Joao R.} and Tatu Rimpil{\"a}inen and Elina Siev{\"a}nen and Kari Rissanen and Afonso, {Carlos A.M.} and Candeias, {Nuno R.}",

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T1 - Pot-economy autooxidative condensation of 2-Aryl-2-lithio-1,3-dithianes

AU - Vale, Joao R.

AU - Rimpiläinen, Tatu

AU - Sievänen, Elina

AU - Rissanen, Kari

AU - Afonso, Carlos A.M.

AU - Candeias, Nuno R.

N1 - INT=keb,"Vale, Joao R."

PY - 2018/2/16

Y1 - 2018/2/16

N2 - 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.

AB - 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.

U2 - 10.1021/acs.joc.7b02896

DO - 10.1021/acs.joc.7b02896

M3 - Article

AN - SCOPUS:85042195347

SN - 0022-3263

VL - 83

SP - 1948

EP - 1958

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 4

ER -

Pot-economy autooxidative condensation of 2-Aryl-2-lithio-1,3-dithianes

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