Download PDF
Synlett 2018; 29(17): 2251-2256
DOI: 10.1055/s-0037-1611003
letter
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Copper-Catalyzed C(sp)–H Bond Insertion of Carbenoids Derived from N-Tosylhydrazones

Takao Osako
,
Makoto Nagaosa
,
Go Hamasaka
,
Yasuhiro Uozumi*
Institute for Molecular Science (IMS) and JST-ACCEL, Okazaki, Aichi 444-8787, Japan   Email: uo@ims.ac.jp
› Author AffiliationsThis work was supported by the JST-ACCEL program (JPMJAC401). We are also grateful for funding from the JSPS KAKENHI [Grant-in-Aid for Challenging Exploratory Research (No. 26620090), for Young Scientists (B) (No. 26810099), and for Scientific Research (C) (No. 16K05876)].
Further Information

Publication History

Received: 04 June 2018

Accepted after revision: 05 August 2018

Publication Date:
14 September 2018 (online)

    Permissions and Reprints All articles of this category


Abstract

A chiral copper(I)–phosphoramidite complex efficiently catalyzed the asymmetric insertion of the carbenoids derived from N-tosyl hydrazones into alkyne C–H bonds to give the corresponding chiral alkynylated products in up to 77% yield and with up to 74% ee.

Key words

copper catalysis - asymmetric catalysis - carbenoids - hydrazones - alkynes

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611003.
  • Supporting Information
 

  • References and Notes

    • 1a Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861
      CrossrefPubMed
    • 1b Davies HM. L, Manning JR. Nature 2008; 451: 417
    • 1c Slattery CN, Ford A, Maguire AR. Tetrahedron 2010; 66: 6681
      Crossref
    • 1d Davies HM, Morton D. Chem. Soc. Rev. 2011; 40: 1857
      CrossrefPubMed
    • 1e Archambeau A, Miege F, Meyer C, Cossy J. Acc. Chem. Res. 2015; 48: 1021
      CrossrefPubMed
    • 1f Ford A, Miel H, Ring A, Slattery CN, Maguire AR, McKervey MA. Chem. Rev. 2015; 115: 9981
      CrossrefPubMed
    • 1g Xia Y, Qiu D, Wang J. Chem. Rev. 2017; 117: 13810
      CrossrefPubMed
    • 2a Che J, Xing D, Hu W. Curr. Org. Chem. 2016; 20: 41
      CrossrefPubMed
    • 2b Torres Ó, Pla-Quitana A. Tetrahedron Lett. 2016; 57: 3881
      CrossrefPubMed
    • 2c Suárez A, Fu GC. Angew. Chem. Int. Ed. 2004; 43: 3580
      CrossrefPubMed
    • 2d Hassink M, Liu X, Fox JM. Org. Lett. 2011; 13: 2388
      CrossrefPubMed
    • 2e Xiao Q, Xia Y, Li H, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2011; 50: 1114
      CrossrefPubMed
    • 2f Ye F, Ma X, Xiao Q, Li H, Zhang Y, Wang J. J. Am. Chem. Soc. 2012; 134: 5742
      CrossrefPubMed
    • 2g Hossain ML, Ye F, Zhang Y, Wang J. J. Org. Chem. 2013; 78: 1236
      CrossrefPubMed
    • 2h Li J, Ding D, Liu L, Sun J. RSC Adv. 2013; 3: 21260
      Crossref
    • 2i Xiao T, Zhang P, Xie Y, Wang J, Zhou L. Org. Biomol. Chem. 2014; 12: 6215
      CrossrefPubMed
    • 2j Zhang Z, Zhou Q, Yu W, Li T, Wu G, Zhang Y, Wang J. Org. Lett. 2015; 17: 2474
      CrossrefPubMed
    • 2k Ye F, Wang C, Ma X, Hossain ML, Xia Y, Zhang Y, Wang J. J. Org. Chem. 2015; 80: 647
      CrossrefPubMed
    • 2l Wang C, Ye F, Wu C, Zhang Y, Wang J. J. Org. Chem. 2015; 80: 8748
      CrossrefPubMed
  • 4 Tang Y, Chen Q, Liu X, Wang G, Lin L, Feng X. Angew. Chem. Int. Ed. 2015; 54: 9512
    CrossrefPubMed
    • 5a Zhao X, Zhang Y, Wang J. Chem. Commun. 2012; 48: 10162
      CrossrefPubMed
    • 5b Zhu S.-F, Zhou Q.-L. Acc. Chem. Res. 2012; 45: 1365
      CrossrefPubMed
    • 5c Ren Y.-Y, Zhu S.-F, Zhou Q.-L. Org. Biomol. Chem. 2018; 16: 3087 , See also refs. 1 (a), 1 (c), and 1 (f)
      CrossrefPubMed
  • 6 For our achievements in asymmetric carbenoid insertions into phenolic O–H bonds, see: Osako T, Panichakul D, Uozumi Y. Org. Lett. 2012; 14: 194
    CrossrefPubMed
  • 7 A related investigated was recently reported by Wang and co-workers, see: Chu W.-D, Guo F, Yu L, Hong J, Liu Q, Mo F, Zhang Y, Wang J. Chin. J. Chem. 2018; 36: 217
    Crossref
    • 8a Fulton JR, Aggarwal VK, de Vicente J. Eur. J. Org. Chem. 2005; 1479
    • 8b Shao Z, Zhang H. Chem. Soc. Rev. 2012; 41: 560
      CrossrefPubMed
    • 8c Xiao Q, Zhang Y, Wang J. Acc. Chem. Res. 2013; 46: 236
      CrossrefPubMed
  • 9 The ee value of 3cB could not be determined directly, consequently, the ee value was determined after derivatization to 1,1′-(but-1-yne-1,3-diyl)dibenzene (4) as shown in Scheme 3.
  • 10 Galdi N, Della Monica C, Spinella A, Oliva L. J. Mol. Catal. A: Chem. 2006; 243: 106
    Crossref
  • 11 Wang T, Wang M, Fang S, Liu J.-y. Organometallics 2014; 33: 3941
    Crossref
  • 12 Frisch MJ, Trucks GW, Schlegel HB. et al. Gaussian 09 (Revision D.01). Gaussian, Inc.; Wallingford: 2016
    Google Scholar
  • 13 Asymmetric Insertion Reactions; General ProcedureA mixture of CuI (1.9 mg, 10 μmol), (S)-Monophos (7.9 mg, 22 μmol), and Cs2CO3 (176 mg, 0.54 mmol) in 1,4-dioxane (2 mL) under N2 was stirred at r.t. for 30 min. Hydrazone 1 (0.3 mmol) and alkyne 2 (0.2 mmol) were added, and the mixture was heated to 80 °C for 24 h. The resulting suspension was passed through short plug of silica gel (eluent: EtOAc), concentrated, and purified by preparative TLC and gel-permeation chromatography to give the corresponding insertion products. tert-Butyl[(3S)-3-(1-naphthyl)but-1-yn-1-yl]diphenylsilane (3aA)Colorless oil; yield: 64.5 mg (77%, 58% ee); [α]D 25 = +6.9 (c 0.37, CHCl3). 1H NMR (396 MHz, CDCl3): δ = 8.15 (d, J = 8.7 Hz, 1 H), 7.80–7.89 (m, 6 H), 7.75 (d, J = 8.7 Hz, 1 H), 7.43–7.54 (m, 3 H), 7.30–7.40 (m, 6 H), 4.70 (q, J = 7.1 Hz, 1 H), 1.75 (d, J = 7.1 Hz, 3 H), 1.10 (s, 9 H). 13C{1H} NMR (100 MHz, CDCl3): δ = 138.6, 135.8, 134.2, 133.9, 130.6, 129.6, 129.2, 127.8, 127.7, 126.2, 125.8, 125.7, 124.6, 123.4, 114.2, 82.1, 30.0, 27.3, 23.7, 18.7. HRMS (APCI): m/z [M + H]+ calcd for C30H31Si: 419.2195; found: 419.2203. HPLC: ChiralPak AD-H column (hexane, flow rate 0.5 mL/min, λ = 280 nm); t R = 13.7 min (minor isomer; integration: 322916 μV·s); t R = 17.4 min (major isomer; integration: 1223585 μV·s).