Synthesis 2020; 52(06): 847-852
DOI: 10.1055/s-0039-1690730
psp
© Georg Thieme Verlag Stuttgart · New York

Gram-Scale Synthesis of the Co(nmp)2 Catalyst to Prepare trans-2,5-Disubstituted Tetrahydrofurans by the Aerobic Oxidative Cyclization of Pent-4-en-1-ols

Barbora Morra
,
Nicholas A. Morra
,
Daniel G. MacDonald
,
Brian L. Pagenkopf
Department of Chemistry, The University of Western Ontario, 1151 Richmond Street, London, ON N6A 5B7, Canada   Email: [email protected]
› Author Affiliations
We thank the University of Western Ontario, WSS NSERC Bridge (Grant 47229) and the Natural Sciences and Engineering Research Council of Canada (NSERC) (DG RGPIN-2014-04891) for financial support. B.M. and N.A.M. thank NSERC for Vanier and CGSD Scholarships support, respectively.
Further Information

Publication History

Received: 01 September 2019

Accepted after revision: 03 October 2019

Publication Date:
08 January 2020 (online)


Abstract

Co(nmp)2 is an efficient catalyst for the aerobic oxidative cyclization of pent-4-en-1-ols to give 5-hydroxymethyl trans-tetrahydrofurans (THFs) as single diastereomers in high yield. The trans-THF pharmacophore is of interest because it is found in many biologically active natural products. The three-step synthesis of Co(nmp)2 described here gives the catalyst as a fine powder in 80–85% overall yield on 10-gram scale. The use of the catalyst in a representative oxidative cyclization is also described.

Supporting Information

 
  • References

  • 1 Current address: Department of Chemistry, University of Toronto, 80 St. George Street, LM 114, Toronto, ON M5S 3H6, Canada.
    • 2a Bermejo A, Figadere B, Zafra-Polo M.-C, Barrachina I, Estornell E, Cortes D. Nat. Prod. Rep. 2005; 22: 269
    • 2b Spurr IB, Brown RC. D. Molecules 2010; 15: 460
    • 5a Miller Y, Miao L, Hosseini AS, Chemler SR. J. Am. Chem. Soc. 2012; 134: 12149
    • 5b Hartung J, Drees S, Greb M, Schmidt P, Svoboda I, Fuess H, Murso A, Stalke D. Eur. J. Org. Chem. 2003; 2388
  • 7 Li W, Jia P, Han B, Li D, Yu W. Tetrahedron 2013; 69: 3274
    • 8a Schuch D, Fries P, Dönges M, Menendez Perez B, Hartung J. J. Am. Chem. Soc. 2009; 131: 12918
    • 8b Menendez Perez B, Hartung J. Tetrahedron Lett. 2009; 50: 960
    • 8c Fries P, Halter D, Kleinschek A, Hartung J. J. Am. Chem. Soc. 2011; 133: 3906
    • 8d Fries P, Mueller MK, Hartung J. Org. Biomol. Chem. 2013; 11: 2630
  • 9 Wu D, Forsyth CJ. Org. Lett. 2013; 15: 1178
    • 10a Wang Z.-M, Tian S.-K, Shi M. Tetrahedron: Asymmetry 1999; 10: 667
    • 10b Wang Z.-M, Tian S.-K, Shi M. Chirality 2000; 12: 581
  • 11 Wang Z.-M, Tian S.-K, Shi M. Eur. J. Org. Chem. 2000; 349
  • 12 Evans PA, Cui J, Gharpure SJ, Polosukhin A, Zhang H.-R. J. Am. Chem. Soc. 2003; 125: 14702
  • 13 Zhao H, Gorman JS. T, Pagenkopf BL. Org. Lett. 2006; 8: 4379
  • 14 Wang J, Pagenkopf BL. Org. Lett. 2007; 9: 3703
  • 15 Chen Z, Sinha SC. Tetrahedron Lett. 2009; 50: 6398
    • 16a Morra NA, Pagenkopf BL. Org. Lett. 2011; 13: 572
    • 16b Morra NA, Pagenkopf BL. Eur. J. Org. Chem. 2013; 756
    • 16c Morra NA, Pagenkopf BL. Tetrahedron 2013; 69: 8632
    • 17a Valot G, Regens CS, O’Malley DP, Godineau E, Takikawa H, Furstner A. Angew. Chem. Int. Ed. 2013; 52: 9534
    • 17b Valot G, Maihol D, Regens CS, O’Malley DP, Godineau E, Takikawa H, Petra P, Fürstner A. Chem. Eur. J. 2015; 21: 2398
  • 18 Dias LC, Ferreira MA. B. J. Org. Chem. 2012; 77: 4046
  • 19 Dias LC, Farina LS, Ferreira MA. B. Braz. Chem. Soc. 2013; 24: 184
  • 20 Philips GA, Wright TB, Stevens AC, Pagenkopf BL. Can. J. Chem. 2014; 93: 193
  • 21 Philips GA, Palmer C, Stevens AC, Piotrowski ML, Dekruyf DS. R, Pagenkopf BL. Tetrahedron Lett. 2015; 56: 6052
  • 22 Quinn KJ, Hu Y, Miller PJ, Walsh RT, Caporello MA, Maliszewski ML, Markowski JH. Tetrahedron Lett. 2019; 60: 1773
    • 23a Inoki S, Mukaiyama T. Chem. Lett. 1990; 1: 67
    • 23b The asymmetric total synthesis of laurallene was recently reported: Yoshimura F, Okada T, Tanino K. Org. Lett. 2019; 21: 559
  • 24 Wang J, Morra NA, Zhao H, Gorman JS. T, Lynch V, McDonald R, Reichwein JF, Pagenkopf BL. Can. J. Chem. 2009; 87: 328
  • 25 Palmer C, Morra NA, Stevens AC, Bajtos B, Machin BP, Pagenkopf BL. Org. Lett. 2009; 11: 5614
  • 26 tert-Butyl hydroperoxide in isooctane was prepared according to a previously reported procedure: Gao YG, Hanson JM, Ko SY, Masamune H, Sharpless KB. J. Am. Chem. Soc. 1987; 109: 5765