Synthesis
DOI: 10.1055/s-0039-1690741
special topic
© Georg Thieme Verlag Stuttgart · New York

Cobalt(III)-Catalyzed Diastereoselective Three-Component C–H Bond Addition to Butadiene and Activated Ketones

Zican Shen
,
Chen Li
,
Brandon Q. Mercado
,
Department of Chemistry, Yale University, New Haven, CT 06520, USA   Email: jonathan.ellman@yale.edu
› Author Affiliations
This work was supported by the National Institutes of Health (R35GM122473).
Further Information

Publication History

Received: 02 October 2019

Accepted after revision: 22 October 2019

Publication Date:
07 November 2019 (online)

Published as part of the Special Topic Domino C–H Functionalization Reaction/Cascade Catalysis

Abstract

A highly diastereoselective three-component C–H bond addition across butadiene and activated ketones is described. This transformation provides homoallylic tertiary alcohols through the formation of two C–C σ-bonds and with complete selectivity for an E-alkene isomer. The reaction exhibits good scope with respect to activated ketone inputs, including highly strained cyclic and electron-deficient cyclic and acyclic ketones. Additionally, high diastereoselectivities were achieved for alcohols prepared from unsymmetrical ketones.

Supporting Information

 
  • References


    • Selected relevant reviews on C–H functionalization:
    • 1a Woźniak Ł, Cramer N. Trends Chem. 2019; 1: 471
    • 1b Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
    • 1c Kim D.-S, Park W.-J, Jun C.-H. Chem. Rev. 2017; 117: 8977
    • 1d Hummel JR, Boerth JA, Ellman JA. Chem. Rev. 2017; 117: 9163
    • 1e Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
    • 1f Yang L, Huang H. Chem. Rev. 2015; 115: 3468
    • 1g Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
    • 1h Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960 ; Angew. Chem. 2012, 124, 9092

      Selected reviews for three-component Catellani-type reactions:
    • 2a Wang J, Dong G. Chem. Rev. 2019; 119: 7478
    • 2b Della Ca’ N, Fontana M, Motti E, Catellani M. Acc. Chem. Res. 2016; 49: 1389
    • 2c Ye J, Lautens M. Nat. Chem. 2015; 7: 863
    • 2d Martins A, Mariampillai B, Lautens M. Top. Curr. Chem. 2010; 292: 1
    • 2e Catellani M. Top. Organomet. Chem. 2005; 14: 21
    • 2f Catellani M, Frignani F, Rangoni A. Angew. Chem., Int. Ed. Engl. 1997; 36: 119 ; Angew. Chem. 1997, 109, 142
    • 3a Pinkert T, Wegner T, Mondal S, Glorius F. Angew. Chem. Int. Ed. 2019; 58: 15041 ; Angew. Chem. 2019, 131, 15183
    • 3b Wang X.-G, Li Y, Liu H.-C, Zhang B.-S, Gou X.-Y, Wang Q, Ma J.-W, Liang Y.-M. J. Am. Chem. Soc. 2019; 141: 13914
    • 3c Maity S, Potter TJ, Ellman JA. Nat. Catal. 2019; 2: 756
    • 3d Yang J, Ji D.-W, Hu Y.-C, Min X.-T, Zhou X, Chen Q.-A. Chem. Sci. 2019; 10: 9560
    • 3e Dongbang S, Shen Z, Ellman JA. Angew. Chem. Int. Ed. 2019; 58: 12590 ; Angew. Chem. 2019, 131, 12720
    • 3f Li R, Ju C.-W, Zhao D. Chem. Commun. 2019; 55: 695
    • 3g Tang M, Li Y, Han S, Liu L, Ackermann L, Li J. Eur. J. Org. Chem. 2019; 660
    • 3h Boerth JA, Maity S, Williams SK, Mercado BQ, Ellman JA. Nat. Catal. 2018; 1: 673
    • 3i Boerth JA, Ellman JA. Angew. Chem. Int. Ed. 2017; 56: 9976 ; Angew. Chem. 2017, 129, 10108
    • 3j Zhang S.-S, Xia J, Wu J.-Q, Liu X.-G, Zhou C.-J, Lin E, Li Q, Huang S.-L, Wang H. Org. Lett. 2017; 19: 5868
    • 3k Boerth JA, Hummel JR, Ellman JA. Angew. Chem. Int. Ed. 2016; 55: 12650 ; Angew. Chem. 2016, 128, 12840
    • 3l Boerth JA, Ellman JA. Chem. Sci. 2016; 7: 1474

      Intermolecular addition of unactivated C–H bonds to ketones to give tertiary alcohols has only been reported for a couple of very highly activated ketones:
    • 4a Jo H, Park J, Choi M, Sharma S, Jeon M, Mishra NK, Jeong T, Han S, Kim IS. Adv. Synth. Catal. 2016; 358: 2714
    • 4b Zhang XS, Zhu QL, Luo FX, Chen GH, Wang X, Shi ZJ. Eur. J. Org. Chem. 2013; 6530
  • 5 Tanaka R, Ikemoto H, Kanai M, Yoshino T, Matsunaga S. Org. Lett. 2016; 18: 5732
  • 6 CCDC 1956911 (4k) and CCDC 1957083 (4l) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 7 Sheldrick GM. Acta Crystallogr., Sect. A 2008; 64: 112