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. 2019 Nov 29;9(67):39119-39123.
doi: 10.1039/c9ra09332j. eCollection 2019 Nov 27.

Sequential cycloaddition and ring expansion reaction of arynes and methylenebenzothiopheneones: synthesis of a benzo-fused eight-membered ring via sulfonium ylides

Peng Xiao  1 , Shikuan Su  1 , Wei Wang  1 , Weiguo Cao  1 , Jie Chen  1 , Jian Li  1 , Yali Chen  1   2
Affiliations

Sequential cycloaddition and ring expansion reaction of arynes and methylenebenzothiopheneones: synthesis of a benzo-fused eight-membered ring via sulfonium ylides

Peng Xiao et al. RSC Adv. .

Abstract

A sequential cycloaddition and ring expansion of arynes and methylenebenzothiopheneones has been disclosed. This strategy proceeds through a sulfonium ylides intermediate and allows for the efficient synthesis of a sulfur-containing benzo-fused eight-membered ring.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Representative natural products and bioactive molecules with sulfur-containing ring.
Scheme 2
Scheme 2. Representative examples involving sulfonium ylide.
Scheme 3
Scheme 3. Substrate scope of the reaction with respect to the methylenebenzothiopheneone. Reaction condition: 1.5 mmol benzyne precursor 1, 1.0 mmol 2-methylenebenzothiophene-3-one 4, CsF (3.0 mmol), in 3 mL DCM. Isolated yields are reported.
Scheme 4
Scheme 4. Reaction conditions: 1.5 mmol naphthyne precursor 6, 1.0 mmol 2-methylenebenzothiophene-3-one 4, CsF (3.0 mmol), in 3 mL DCM. Isolated yields are reported.
Scheme 5
Scheme 5. Control experiments and preliminary mechanistic studies.
Scheme 6
Scheme 6. Possible mechanism.
Scheme 7
Scheme 7. Further application of the products.
See this image and copyright information in PMC

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