Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2020; 52(06): 847-852
DOI: 10.1055/s-0039-1690730
DOI: 10.1055/s-0039-1690730
psp
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
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.
Key words
catalysis - cyclization - furans - green chemistry - heterocycles - ligands - oxygenations - stereoselective synthesisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690730.
- Supporting Information
- CIF File
-
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
- 3a Kobayashi J. In Comprehensive Natural Products Chemistry, Vol. 8. Mori K. Elsevier; New York: 1999: 619
- 3b Ishibashi M, Kobayashi J. Heterocycles 1997; 44: 543
- 3c Kobayashi J. J. Antibiot. 2008; 61: 271
- 4a Kobayashi J, Kubota T. J. Nat. Prod. 2007; 70: 451
- 4b Cardillo G, Orena M. Tetrahedron 1990; 46: 3321
- 4c Wolfe JP, Hay MB. Tetrahedron 2007; 63: 261
- 4d Li N, Shi Z, Tang T, Chen J, Li X. Beilstein J. Org. Chem. 2008; 4: No. 48
- 4e Britton R, Kang B. Nat. Prod. Rep. 2013; 30: 227
- 4f Kang B, Mowat J, Pinter T, Britton R. Org. Lett. 2009; 11: 1717
- 4g Rainier JD. Synthesis of Substituted Tetrahydrofurans. In Synthesis of Saturated Oxygenated Heterocycles I, Topics in Heterocyclic Chemistry, Vol. 35. Cossy J. Springer; Berlin: 2014
- 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
- 6a Perez BM, Schuch D, Hartung J. From Cobalt(II)-Activated Molecular Oxygen to Hydroxymethyl-Substituted Tetrahydrofurans. In Activating Unreactive Substrates: The Role of Secondary Interactions. Bolm C, Hahn FE. Wiley–VCH; Weinheim: 2009: 379-396
- 6b Hartung J, Greb M. J. Organomet. Chem. 2002; 661: 67
- 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