Synthesis 2021; 53(17): 2976-2983
DOI: 10.1055/a-1469-7408
special topic
Bond Activation – in Honor of Prof. Shinji Murai

Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes through Site-Selective C(sp3)–H Bond Activation Triggered by Formation of Rhodacycle

,
Shunki Sakamoto
,
Shuya Agata
,
This work was financially supported by Grants-in-Aid for Scientific Research (B) (No. 20H03360) and Grants-in-Aid for Scientific Research (C) (No. 20K06960) from JSPS. The Nagase Science Technology Foundation (for YS) and the Akiyama Life Science Foundation (for YO) are also acknowledged for financial support.


Abstract

Rhodium(I)-catalyzed enantioselective cyclization of enynes through C(sp3)–H bond activation was investigated. It was found that the cyclization of enynes having a tert-butyl moiety on the alkene afforded a spirocyclic compound (up to 92% ee), while the cyclization of enynes having an isopropyl or an ethyl group on the alkene gave a cyclic diene (up to 98% ee). Furthermore, an intermolecular competition reaction using a deuterium-labeled substrate revealed that C(sp3)–H bond activation was one of the key steps, having a high energy barrier, in this cyclization.

Supporting Information



Publication History

Received: 11 March 2021

Accepted after revision: 30 March 2021

Publication Date:
30 March 2021 (online)

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  • References


    • For selected recent reviews, see:
    • 1a Gutekunst WR, Baran PS. Chem. Soc. Rev. 2011; 40: 1976
    • 1b McMurray LF, O’Hara L, Gaunt M. Chem. Soc. Rev. 2011; 40: 1885
    • 1c Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
    • 1d Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
    • 1e Hartwig JF. J. Am. Chem. Soc. 2016; 138: 2
    • 1f Davies HM. L, Morton DJ. J. Org. Chem. 2016; 81: 343
    • 1g Saint-Denis TG, Zhu R.-Y, Chen G, Wu Q.-F, Yu J.-Q. cience 2018; 359: 747
  • 2 Oonishi Y, Kitano Y, Sato Y. Angew. Chem. Int. Ed. 2012; 51: 7305
  • 3 For an example of Rh(I)-catalyzed cyclization through C(sp3)–H bond activation triggered by formation of rhodacycle, see: Mukai C, Ohta Y, Oura Y, Kawaguchi Y, Inagaki F. J. Am. Chem. Soc. 2012; 134: 19580 

    • For selected examples of Rh(I)-catalyzed cyclization through C(sp2)–H bond activation triggered by formation of rhodacycle, see:
    • 4a Tanaka K, Otake Y, Wada A, Noguchi K, Hirano M. Org. Lett. 2007; 9: 2203
    • 4b Tsuchikama K, Kuwata Y, Tahara Y, Yoshinami Y, Shibata T. Org. Lett. 2007; 9: 3097
    • 4c Tanaka K, Otake Y, Sagae H, Noguchi K, Hirano M. Angew. Chem. Int. Ed. 2008; 47: 1312
    • 4d Kawaguchi Y, Yasuda S, Kaneko A, Oura Y, Mukai C. Angew. Chem. Int. Ed. 2014; 53: 7608
    • 4e Kawaguchi Y, Yasuda S, Mukai C. Angew. Chem. Int. Ed. 2016; 55: 10473
    • 4f Kawaguchi Y, Yasuda S, Mukai C. J. Org. Chem. 2017; 82: 7666

      For selected examples of Rh(I)-catalyzed enantioselective cycloisomerization of enynes through oxidative cyclization, see:
    • 5a Cao P, Wang B, Zhang X.-M. J. Am. Chem. Soc. 2000; 122: 6490
    • 5b Lei A, He M, Zhang X. J. Am. Chem. Soc. 2002; 124: 8198
    • 5c Mikami K, Yusa Y, Hatano M, Wakabayashi K, Aikawa K. Tetrahedron 2004; 60: 4475
    • 5d Nicolaou KC, Li A, Ellery SP, Edmonds DJ. Angew. Chem. Int. Ed. 2009; 48: 6293
    • 5e Masutomi K, Noguchi K, Tanaka K. J. Am. Chem. Soc. 2014; 136: 7627
    • 5f Deng X, Ni S.-F, Han Z.-Y, Guan Y.-Q, Lv H, Dang L, Zhang X.-M. Angew. Chem. Int. Ed. 2016; 55: 6295

    • For an example of Rh(I)-catalyzed enantioselective Pauson–Khand-Type reaction of enynes through oxidative cyclization, see:
    • 5g Jeong N, Sung BK, Choi YK. J. Am. Chem. Soc. 2000; 122: 6771

    • For selected examples of Rh(I)-catalyzed enantioselective [2+2+2] cycloaddition of enynes through oxidative cyclization, see:
    • 5h Shibata T, Arai Y, Tahara Y. Org. Lett. 2005; 7: 4955
    • 5i Evans PA, Lai KW, Sawyer JR. J. Am. Chem. Soc. 2005; 127: 12466
    • 5j Shibata T, Tahara Y. J. Am. Chem. Soc. 2006; 128: 11766
    • 5k Shibata T, Tahara Y, Tamura K, Endo K. J. Am. Chem. Soc. 2008; 130: 3451
    • 5l Ishida M, Shibata Y, Noguchi K, Tanaka K. Chem. Eur. J. 2011; 17: 12578
    • 5m Suda T, Noguchi K, Tanaka K. Angew. Chem. Int. Ed. 2011; 50: 4475
    • 5n Masutomi K, Sakiyama N, Noguchi K, Tanaka K. Angew. Chem. Int. Ed. 2012; 51: 13031
    • 5o Yoshizaki S, Nakamura Y, Masutomi K, Yoshida T, Noguchi K, Shibata Y, Tanaka K. Org. Lett. 2016; 18: 388
    • 5p Masutomi K, Sugiyama H, Uekusa H, Shibata Y, Tanaka K. Angew. Chem. Int. Ed. 2016; 55: 15373
    • 5q Ueda H, Masutomi K, Shibata Y, Tanaka K. Org. Lett. 2017; 19: 2913
    • 5r See also ref. 4c

      For our recent studies on Rh(I)-catalyzed cyclization through oxidative addition of two C–C multiple bonds, see:
    • 6a Oonishi Y, Kitano Y, Sato Y. Tetrahedron 2013; 69: 7713
    • 6b Oonishi Y, Yokoe T, Hosotani A, Sato Y. Angew. Chem. Int. Ed. 2014; 53: 1135
    • 6c Oonishi Y, Hato Y, Sato Y. Adv. Synth. Catal. 2015; 357: 3033
    • 6d Oonishi Y, Hato Y, Sato Y. Adv. Synth. Catal. 2016; 358: 2273
    • 6e Hato Y, Oonishi Y, Yamamoto Y, Nakajima K, Sato Y. J. Org. Chem. 2016; 81: 7847
  • 7 For our recent study on Rh(I)-catalyzed asymmetric cyclization of enyne through O–H bond activation, which was triggered by the formation of the rhodacycle, see: Oonishi Y, Masusaki S, Sakamoto S, Sato Y. Angew. Chem. Int. Ed. 2019; 58: 8736
  • 8 The geometry of alkene in the cyclic compound 4a was determined by NOESY. The absolute configuration of 4a and 5a was not determined.
  • 9 Compound 4a was subjected to the standard reaction conditions, giving 5a in 80% yield (Scheme 7).

    • For selected examples of the cyclizations with the formation of 4-membered carbocyclic compound through C(sp3)–H bond activation, see:
    • 10a Chaumontet M, Piccardi R, Audic N, Hitce J, Peglion J.-L, Clot E, Baudoin O. J. Am. Chem. Soc. 2008; 130: 15157
    • 10b Rousseaux S, Davi M, Sofack-Kreutzer J, Pierre C, Kefalidis CE, Clot E, Fagnou K, Baudoin O. J. Am. Chem. Soc. 2010; 132: 10706
    • 10c Kefalidis CE, Davi M, Holstein PM, Clot E, Baudoin O. J. Org. Chem. 2014; 79: 11903
  • 11 The effect of the counter anion (X) of a cationic Rh(I) complex on the reactivity was investigated using a [Rh(cod)2]X (X = ClO4, PF6, SbF6, and BArF 4). However, these anions showed almost the same reactivity as those using BF4 in this cyclization.
  • 12 Huang studied the mechanism for Rh(I)-catalyzed cyclization of allenyne through C(sp3)–H bond activation (ref. 2) by means of DFT calculation. According to this work, the cyclization proceeded through metal-assisted σ-bond metathesis like rhoda­cycle iv, see: Huang G. Org. Lett. 2015; 17: 1994

    • For recent reviews, see:
    • 13a Gómez-Gallego M, Sierra MA. Chem. Rev. 2011; 111: 4857
    • 13b Simmons EM, Hartwig JF. Angew. Chem. Int. Ed. 2012; 51: 3066