Iron(III)-Catalyzed Prins Cyclization towards the Synthesis of trans-Fused Bicyclic Tetrahydropyrans

Abstract

trans-Fused bicyclic tetrahydropyrans have been synthesized through an intramolecular Prins cyclization catalyzed by iron(III). The cyclization process is stereoselective, leading exclusively to an all-cis configuration in the newly generated ring. This useful methodology allows for easy access to a variety of bicyclic ethers present in a wide range of bioactive natural products. Remarkably, the cyclization reaction works well when more challenging aldehydes bearing a functional group, such as a double bond or an acetate, are used. In addition, we present a computational study which rationalizes the results and explains the complete cis stereoselectivity in the newly formed tetrahydropyran ring.

Key words

iron - cyclic ethers - sustainable metal catalysis - bicyclic tetrahydropyrans - Prins cyclization

• References

• 1a Plietker B. Synlett 2010; 2049
• 1b Holzwarth MS, Plietker B. ChemCatChem 2013; 5: 1650
• 2a Enthaler S, Junge K, Beller M. Angew. Chem. Int. Ed. 2008; 47: 3317
• 2b Czaplik WM, Mayer M, Cvengroš J, von Wangelin AJ. ChemSusChem 2009; 2: 396
• 3a Miranda PO, Ramírez MA, Martín VS, Padrón JI. Org. Lett. 2006; 8: 1633
• 3b Carballo RM, Ramírez MA, Rodríguez ML, Martín VS, Padrón JI. Org. Lett. 2006; 8: 3837
• 3c Carballo RM, Purino M, Ramírez MA, Martín VS, Padrón JI. Org. Lett. 2010; 12: 5334
• 3d Purino MA, Ramírez MA, Daranas AH, Martín VS, Padrón JI. Org. Lett. 2012; 14: 5904
• 4a Miranda PO, Diaz DD, Padrón JI, Bermejo J, Martín VS. Org. Lett. 2003; 5: 1979
• 4b Miranda PO, León LG, Martín VS, Padrón JI, Padrón JM. Bioorg. Med. Chem. Lett. 2006; 16: 3135
• 4c Miranda PO, Carballo RM, Martín VS, Padrón JI. Org. Lett. 2009; 11: 357
• 5 Rutkowski J, Brzezinski B. Biomed. Res. Int. 2013; 162513
• 6 Kadota I, Yamamoto Y. Acc. Chem. Res. 2005; 38: 423
• 7 Wang BG, Gloer JB, Ji NY, Zhao JC. Chem. Rev. 2013; 113: 3632
• 8a Nakata T. Chem. Rev. 2005; 105: 4314
• 8b Nakata T. Chem. Soc. Rev. 2010; 39: 1955
• 8c Inoue M. Chem. Rev. 2005; 105: 4379
• 8d Vilotijevic I, Jamison TF. Angew. Chem. Int. Ed. 2009; 48: 5250
• 8e Deiters A, Martin SF. Chem. Rev. 2004; 104: 2199
• 8f Álvarez E, Candenas ML, Pérez R, Ravelo JL, Martín JD. Chem. Rev. 1995; 95: 1953
• 8g Morris JC, Phillips AJ. Nat. Prod. Rep. 2011; 28: 269 ; and previous issues in the series
• 9 Martín T, Padrón JI, Martín VS. Synlett 2014; 25: 12
• 10 Nakata T. Chem. Soc. Rev. 2010; 39: 1955 ; and references cited therein
• 11a Nicolaou KC, Nugiel DA, Couladouros E, Hwang C.-K. Tetrahedron 1990; 46: 4517
• 11b Nicolaou KC, Bunnage ME, McGarry DG, Shi S, Somers PK, Wallace PA, Chu X.-J, Agrios KA, Gunzner JL, Yang Z. Chem. Eur. J. 1999; 5: 599
• 11c Nicolaou KC, Wallace PA, Shi S, Ouellette MA, Bunnage ME, Gunzner JL, Agrios KA, Shi G.-q, Gärtner P, Yang Z. Chem. Eur. J. 1999; 5: 618
• 11d Nicolaou KC, Shi G.-Q, Gunzner JL, Gärtner P, Wallace PA, Ouellette MA, Shi S, Bunnage ME, Agrios KA, Veale CA, Hwang C.-K, Hutchinson J, Prasad CV. C, Ogilvie WW, Yang Z. Chem. Eur. J. 1999; 5: 628
• 11e Álvarez E, Díaz MT, Pérez R, Ravelo JL, Regueiro A, Vera JA, Zurita D, Martín JD. J. Org. Chem. 1994; 59: 2848
• 11f Mori Y, Hayashi H. Tetrahedron 2002; 58: 1789
• 11g Kadota I, Kadowaki C, Park C.-H, Takamura H, Sato K, Chan PW. H, Thorand S, Yamamoto Y. Tetrahedron 2002; 58: 1799
• 11h Hori N, Matsukura H, Matsuo G, Nakata T. Tetrahedron 2002; 58: 1853
• 11i Kira K, Hamajima A, Isobe M. Tetrahedron 2002; 58: 1875
• 11j Sasaki M, Ishikawa M, Fuwa H, Tachibana K. Tetrahedron 2002; 58: 1889
• 11k Candenas ML, Pinto FM, Cintado CG, Morales EQ, Brouard I, Díaz MT, Rico M, Rodríguez E, Rodríguez RM, Pérez R, Pérez RL, Martín JD. Tetrahedron 2002; 58: 1921
• 11l Clark JS, Elustondo F, Trevitt GP, Boyall D, Robertson J, Blake AJ, Wilson C, Stammen B. Tetrahedron 2002; 58: 1973
• 11m Ajarilla A, Plumet J. Synthesis 2008; 3516
• 12 To the best of our knowledge, there is only one example of a carbohydrate-based Prins cyclization, for the synthesis of a sugar-based furan–tetrahydropyran; see: Yadav JS, Reddy BV. S, Singh AP, Chaya DN, Chatterjee D, Kunwar AC. Tetrahedron Lett. 2010; 51: 1475
• 13a Nicolaou KC, Hwang CK, Marron BE, DeFrees SA, Couladouros EA, Abe Y, Carroll PJ, Snyder JP. J. Am. Chem. Soc. 1990; 112: 3040
• 13b Álvarez E, Delgado M, Díaz MT, Hanxing L, Pérez R, Martín JD. Tetrahedron Lett. 1996; 37: 2865
• 13c Carrillo R, Martín VS, López M, Martín T. Tetrahedron 2005; 61: 8177
• 14 Bereczki I, Kicsák M, Dobray L, Borbás A, Batta G, Kéki S, Nikodém EN, Ostorházi E, Rozgonyi F, Vanderlinden E, Naesens L, Herczegh P. Bioorg. Med. Chem. Lett. 2014; 24: 3251
• 15 The synthesis of trans-fused bicyclic tetrahydropyran 10 using FeCl₃ with TMSCl led to a 50% yield.
• 16 For computational details, see the Supporting Information.

Similar intermediates have been proposed in closely related Prins cyclizations; see, for instance:
• 17a Alder RW, Harvery JN, Oakley MT. J. Am. Chem. Soc. 2002; 124: 4960
• 17b Jasti R, Rychnovsky SD. J. Am. Chem. Soc. 2006; 128: 13640