Synlett 2019; 30(20): 2203-2208
DOI: 10.1055/s-0039-1690212
synpacts
© Georg Thieme Verlag Stuttgart · New York

[3,3]- and [5,5]-Sigmatropic Rearrangements of Aryl Sulfoxides Using An ‘Assembly/Deprotonation’ Technology

Lei Zhang
,
Mengjie Hu
,
Bo Peng
This work is supported by Zhejiang Normal University and the National Natural Science Foundation of China (Grant No. 21502171).
Further Information

Publication History

Received: 26 August 2019

Accepted after revision: 07 October 2019

Publication Date:
17 October 2019 (online)

Abstract

The redox-neutral ortho-functionalizations of aryl/heteroaryl sulfoxides via interrupted Pummerer processes have been greatly advanced since its discovery by Kita and Padwa in the early 2000s. In this context, we recently developed an ortho-cyanoalkylation of aryl sulfoxides with alkyl nitriles using an ‘assembly/deprotonation’ protocol. The success of the reaction hinges on the independent control of the electrophilic assembly of both coupling partners and subsequent deprotonation of the in situ generated imine sulfonium intermediates. Further [3,3]-sigmatropic rearrangement of the in situ formed ketenimine sulfonium species furnishes ortho-cyanoalkylated aryl sulfides. More recently, we also applied the ‘assembly/deprotonation’ strategy for the development of the [5,5]-sigmatropic rearrangement of aryl sulfoxides with allyl nitriles that allows for para-cyanoalkylation of aryl sulfoxides. The development of these two reactions is described in this Synpacts article.

1 Background

2 [3,3]-Sigmatropic Rearrangement

3 [5,5]-Sigmatropic Rearrangement

4 Conclusion

 
  • References

    • 1a Kaiser D, Klose I, Oost R, Neuhaus J, Maulide N. Chem. Rev. 2019; 119: 8701
    • 1b Smith LH. S, Coote SC, Sneddon HF, Proctor DJ. Angew. Chem. Int. Ed. 2010; 49: 5832
    • 1c Akai S, Kita Y. Top. Curr. Chem. 2007; 274: 35
    • 1d Feldman KS. Tetrahedron 2006; 62: 5003
    • 1e Bur SK, Padwa A. Chem. Rev. 2004; 104: 2401
    • 2a Akai S, Kawashita N, Wada Y, Satoh H, Alinejad AH, Kakiguchi K, Kuriwaki I, Kita Y. Tetrahedron Lett. 2006; 47: 1881
    • 2b Padwa A, Nara S, Wang Q. Tetrahedron Lett. 2006; 47: 595
    • 2c Akai S, Kawashita N, Satoh H, Wada Y, Kakiguchi K, Kuriwaki I, Kita Y. Org. Lett. 2004; 6: 3793
    • 3a Shrives HJ, Fernández-Salas JA, Hedtke C, Pulis AP, Procter DJ. Nat. Commun. 2017; 8: 14801
    • 3b Eberhart AJ, Cicoira C, Procter DJ. Org. Lett. 2013; 15: 3994
    • 3c Eberhart AJ, Imbriglio JE, Procter DJ. Org. Lett. 2011; 13: 5882
    • 3d For an elegant example of [3,3]-rearrangement of allyl sulfoxides with electron-rich heteroarenes, see: Šiaučiulis M, Sapmaz S, Pulis AP, Procter DJ. Chem. Sci. 2018; 9: 754
    • 4a He Z, Shrives HJ, Fernández-Salas JA, Abengózar A, Neufeld J, Yang K, Pulis AP, Procter DJ. Angew. Chem. Int. Ed. 2018; 57: 5759
    • 4b Eberhart AJ, Shrives H, Zhang Y, Carrër A, Parry AV. S, Tate DJ, Tumer ML, Procter DJ. Chem. Sci. 2016; 7: 1281
    • 4c Eberhart AJ, Shrives HJ, Álvarez E, Carrër A, Zhang Y, Procter DJ. Chem. Eur. J. 2015; 21: 7428
    • 4d Eberhart AJ, Procter DJ. Angew. Chem. Int. Ed. 2013; 52: 4008
  • 5 Fernández-Salas JA, Eberhart AJ, Procter DJ. J. Am. Chem. Soc. 2016; 138: 790
    • 6a Huang X, Patil M, Farès C, Thiel W, Maulide N. J. Am. Chem. Soc. 2013; 135: 7312
    • 6b Huang X, Maulide N. J. Am. Chem. Soc. 2011; 133: 8510
    • 7a Yang K, Pulis AP, Perry GJ. P, Procter DJ. Org. Lett. 2018; 20: 7498
    • 7b Yanagi T, Otsuka S, Kasuga Y, Fujimoto K, Murakami K, Nogi K, Yorimitsu H, Osuka A. J. Am. Chem. Soc. 2016; 138: 14582
    • 8a Luo F, Lu Y, Hu M, Tian J, Zhang L, Bao W, Yan C, Huang X, Wang Z.-X, Peng B. Org. Chem. Front. 2018; 5: 1756
    • 8b For a related example of [3,3]-rearrangement of aryl iodanes with α-stannyl nitriles, see: Tian J, Luo F, Zhang C, Huang X, Zhang Y, Zhang L, Kong L, Hu X, Wang Z.-X, Peng B. Angew. Chem. Int. Ed. 2018; 57: 9078
    • 9a Pégot B, Urban C, Diter P, Magnier E. Eur. J. Org. Chem. 2013; 7800
    • 9b Macé Y, Urban C, Pradet C, Blazejewski J.-C, Magnier E. Eur. J. Org. Chem. 2009; 5313
  • 10 Chen D, Fu Y, Cao X, Luo J, Wang F, Huang S. Org. Lett. 2019; 21: 5600 ; in addition to [3,3]-sigmatropic rearrangement, the reaction of cyclopropanols with activated sulfoxides may also proceed via an intramolecular nucleophilic addition process

    • For selected reviews on ortho-functionalization of aryl sulfoxides, see:
    • 11a He Z, Pulis AP, Perry GJ. P, Procter DJ. Phosphorus, Sulfur Silicon Relat. Elem. 2019; 194: 669
    • 11b Yanagi T, Nogi K, Yorimitsu H. Tetrahedron Lett. 2018; 59: 2951
    • 11c Tian Z.-Y, Hu Y.-T, Teng H.-B, Zhang C.-P. Tetrahedron Lett. 2018; 59: 299
    • 11d Yorimitsu H. Chem. Rec. 2017; 17: 1156
    • 11e Shafir A. Tetrahedron Lett. 2016; 57: 2673
    • 11f Pulis AP, Procter DJ. Angew. Chem. Int. Ed. 2016; 55: 9842
    • 11g Huang X, Klimczyk S, Maulide N. Synthesis 2012; 44: 175

      For electrophilic rearrangement of ketene dithioacetal monoxides, see:
    • 12a Okamoto K, Hori M, Yanagi T, Murakami K, Nogi K, Yorimitsu H. Angew. Chem. Int. Ed. 2018; 57: 14230
    • 12b Murakami K, Yorimitsu H, Osuka A. Angew. Chem. Int. Ed. 2014; 53: 7510
    • 12c Murakami K, Yorimitsu H, Osuka A. Bull. Chem. Soc. Jpn. 2014; 87: 1349
    • 12d Ookubo Y, Wakamiya A, Yorimitsu H, Osuka A. Chem. Eur. J. 2012; 18: 12690
    • 12e Kobatake T, Fujino D, Yoshida S, Yorimitsu H, Oshima K. J. Am. Chem. Soc. 2010; 132: 11838
    • 12f Kobatake T, Yoshida S, Yorimitsu H, Oshima K. Angew. Chem. Int. Ed. 2010; 49: 2340
    • 12g Yoshida S, Yorimitsu H, Oshima K. Org. Lett. 2009; 11: 2185

      For [3,3]-rearrangement reactions via the addition of aryl/vinyl sulfoxides to vinyl cation intermediates, see:
    • 13a Kaldre D, Klose I, Maulide N. Science 2018; 361: 664
    • 13b Baldassari LL, Mantovani AC, Senoner S, Maryasin B, Maulide N, Lüdtke DS. Org. Lett. 2018; 20: 5881
    • 13c Kaldre D, Maryasin B, Kaiser D, Gajsek O, González L, Maulide N. Angew. Chem. Int. Ed. 2017; 56: 2212
    • 13d Kaiser D, Veiros LF, Maulide N. Adv. Synth. Catal. 2017; 359: 64
    • 13e Hu L, Gui Q, Chen X, Tan Z, Zhu G. J. Org. Chem. 2016; 81: 4861
    • 13f Peng B, Geerdink D, Farès C, Maulide N. Angew. Chem. Int. Ed. 2014; 53: 5462
    • 13g Peng B, Huang X, Xie L.-G, Maulide N. Angew. Chem. Int. Ed. 2014; 53: 8718

      For selected examples of sulfonium-based [2,3]-sigmatropic rearrangement reactions, see:
    • 14a Zhang Z, Luo Y, Du H, Xu J, Li P. Chem. Sci. 2019; 10: 5156
    • 14b Zhang Z, He P, Du H, Xu J, Li P. J. Org. Chem. 2019; 84: 4517
    • 14c Hu G, Xu J, Li P. Org. Chem. Front. 2018; 5: 2167
    • 14d Zhang Z, Du H, Xu J, Li P. Chem. Commun. 2016; 52: 11547
    • 14e Hu G, Xu J, Li P. Org. Lett. 2014; 16: 6036
  • 15 Shang L, Chang Y, Luo F, He J.-N, Huang X, Zhang L, Kong L, Li K, Peng B. J. Am. Chem. Soc. 2017; 139: 4211
  • 16 Zhang L, He J.-N, Liang Y, Hu M, Shang L, Huang X, Kong L, Wang Z.-X, Peng B. Angew. Chem. Int. Ed. 2019; 58: 5316
    • 17a Yoo JB, Park S.-W, Kang HN, Mondkar HS, Sohn K, Kim H.-M, Kim K.-B, Lee H. Polymer 2014; 55: 3599
    • 17b Liu G, Mori S, Wang X, Noritake S, Tokunaga E, Shibata N. New J. Chem. 2012; 36: 1769
    • 17c Prakash GK. S, Ledneczki I, Chacko S, Olah GA. Org. Lett. 2008; 10: 557
    • 18a Walters MA. J. Org. Chem. 1996; 61: 978
    • 18b Walters MA. J. Am. Chem. Soc. 1994; 116: 11618