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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.
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References

    1. Ilardi E. A. Vitaku E. Njardarson J. T. J. Med. Chem. 2014;57:2832. doi: 10.1021/jm401375q. - DOI - PubMed
    2. Sulfur Compounds: Advances in Research and Application, ed. A. Q. Acton, Scholarly Editions, Atlanta, GA, 2012
    1. Please find the data reflecting the top 200 rankings from http://www.pharmacytimes.com/publications/issue/2012/July2012/Top-200-Dr..., 2012
    1. Asano K. Matsubara S. ACS Catal. 2018;8:6273. doi: 10.1021/acscatal.8b00908. - DOI
    2. Kugita H. Inoue H. Ikezaki M. Konda M. Takeo S. Chem. Pharm. Bull. 1970;18:2284. doi: 10.1248/cpb.18.2284. - DOI
    1. He W. Zhang Z. Ma D. Angew. Chem., Int. Ed. 2019;58:3972. doi: 10.1002/anie.201900035. - DOI - PubMed
    2. Chen J. Chen X. Bois-Choussy M. Zhu J. J. Am. Chem. Soc. 2006;128:87. doi: 10.1021/ja0571794. - DOI - PubMed

    1. For selected reviews on aryne chemistry, see:

    2. Takikawa H. Nishii A. Sakai T. Suzuki K. Chem. Soc. Rev. 2018;47:8030. doi: 10.1039/C8CS00350E. - DOI - PubMed
    3. Roy T. Biju A. T. Chem. Commun. 2018;54:2580. doi: 10.1039/C7CC09122B. - DOI - PubMed
    4. Shi J. Li Y. Li Y. Chem. Soc. Rev. 2017;46:1707. doi: 10.1039/C6CS00694A. - DOI - PubMed
    5. Yoshida S. Hosoya T. Chem. Lett. 2015;44:1450. doi: 10.1246/cl.150839. - DOI
    6. Pérez D. Peña D. Guitián E. Eur. J. Org. Chem. 2013:5981. doi: 10.1002/ejoc.201300470. - DOI
    7. Gampe C. M. Carreira E. M. Angew. Chem., Int. Ed. 2012;51:3766. doi: 10.1002/anie.201107485. - DOI - PubMed
    8. Tadross P. M. Stoltz B. M. Chem. Rev. 2012;112:3550. doi: 10.1021/cr200478h. - DOI - PubMed
    9. Bhunia A. Yetra S. R. Biju A. T. Chem. Soc. Rev. 2012;41:3140. doi: 10.1039/C2CS15310F. - DOI - PubMed