Catalytic Ring Expansion Adventures

Abstract

This account summarizes the Njardarson group ring expansion journey from early vinyl oxirane explorations to the latest vinyl oxetane ring expansion discoveries. The evolution of the program and incredible success of Cu(hfacac)₂ as catalyst is detailed. Application of these new ring expansion reactions to natural product, pharmaceutical and commodity chemical targets is discussed as well as our intriguing mechanistic journey and interesting entry into the world of chiral counterion catalysis.

Key words

ring expansion - catalysis - strained rings - thiiranes - aziridines - oxiranes - oxetanes

• References and Notes

• 1 For a recent example, see: Lautens M, Ouellet SG, Raeppel S. Angew. Chem. Int. Ed. 2000; 39: 4079 ; and references cited therein
• 2 Crawford RJ, Lutener SB, Cockcroft RD. Can. J. Chem. 1976; 54: 3364
• 3a Khumtaveeporn K, Halper H. Acc. Chem. Res. 1995; 28: 414
• 3b Getzler YD. Y. L, Mahadevan V, Lobkovsky EB, Coates GW. J. Am. Chem. Soc. 2002; 124: 1174

Representative patents:
• 4a Besozzi AJ, Cooley SD, Potts FE. III. Petro-Tex Chemical Corporation, Patent US 3812158, 1974 ; Chem. Abstr. 1974, 81, 41287.
• 4b Wall RG, Kurkov VP. Chevron Research Company, Patent US 3996248, 1976 ; Chem. Abstr. 1977, 86, 89592.
• 4c Fischer MBASF. Patent US 5034545, 1991 ; Chem. Abstr. 1991, 115, 30088.
• 4d Monnier JR, Godleski SR, Low HM, McCullough LG, McGarry LW, Phillips GW. Eastman Kodak Company, Patent US 5082956, 1992 ; Chem. Abstr. 1992, 116, 63473.
• 5 Olofsson B, Somfai PVinylepoxides. Aziridines and Epoxides in Organic Synthesis . In Organic Synthesis . Yudin AK. Wiley-VCH; Weinheim: 2006: 315-347
• 6 Batory LA, McInnis CE, Njardarson JT. J. Am. Chem. Soc. 2006; 128: 16054
• 7a 2-Methyltetrahydrofuran is used as a greener replacement for dichloromethane, see: Ripin DH. B, Vetelino M. Synlett 2003; 2353

Representative patents:
• 7b Elliott DC, Frye JG. Battelle Memorial Institute, Patent US 5883266, 1999 ; Chem. Abstr. 1999, 130, 211627.
• 7c Ahmed I. Pure Energy Corporation, Patent US 6852868 B2, 2005 .

Representative patents:
• 8a Weyer H.-J, Fischer R, Merger F, Frank J, Henkelmann J, Siegel H, Ruehl T. BASF, Patent US 5536854, 1996 ; Chem. Abstr. 1996, 126, 167776.
• 8b Takemoto M, Abe T. Mitsubishi Gas Chemical Company, Inc., Patent US 5990324, 1999 ; Chem. Abstr. 1998, 129, 275832.
• 8c Manzer LE. E. I. Du Pont de Nemours and Company, Patent US 2003/0109724 A1, 2003 ; Chem. Abstr. 2003, 139, 38256.
• 8d Beavers WA, Ignatchenko AV. Eastman Kodak Company, Patent US 6812354 B2, 2004 ; Chem. Abstr. 2004, 141, 54185.
• 9 Vollhardt KP. C, Bergman RG. J. Am. Chem. Soc. 1973; 95: 7538
• 10a Adams RD, Long JW. IV, Perrin JL. J. Am. Chem. Soc. 1998; 120: 1922
• 10b Adams RD. Acc. Chem. Res. 2000; 33: 171
• 11 Larksarp C, Sellier O, Alper H. J. Org. Chem. 2001; 66: 3502
• 12 Direct thiirinations are possible, although their development is still in the early stages and existing methods are far from being useful, see: Adam W, Bargon RM. Chem. Rev. 2004; 104: 251
• 13 Maciagiewicz I, Dybowski P, Skowronska A. Tetrahedron Lett. 1999; 40: 3791
• 14 Rogers E, Araki H, Batory LA, McInnis CE, Njardarson JT. J. Am. Chem. Soc. 2007; 129: 2768
• 15 For a recent example, see: Fantauzzi S, Gallo E, Caselli A, Piangiolino C, Ragaini F, Re N, Cenini S. Chem. Eur. J. 2009; 15: 1241
• 16 Heine HW, Fetter ME, Nicholson EM. J. Am. Chem. Soc. 1959; 81: 2202
• 17a Hudlicky T, Frazier JO, Kwart LD. Tetrahedron Lett. 1985; 26: 3523
• 17b Pearson WH. Tetrahedron Lett. 1985; 26: 3527
• 17c Hudlicky T, Frazier JO, Seoane G, Tiedje M, Seoane A, Kwart LD, Beal C. J. Am. Chem. Soc. 1986; 108: 3755
• 17d Pearson WH, Bergmeier SC, Degan S, Lin KC, Poon YF, Schkeryantz JM, Williams JP. J. Org. Chem. 1990; 55: 5719
• 18a Atkinson RS, Rees CW. Chem. Commun. 1967; 1232
• 18b Scheiner P. J. Org. Chem. 1967; 32: 2628
• 18c Logothetis AL. J. Am. Chem. Soc. 1965; 87: 749
• 18d Hirner S, Somfai P. Synlett 2005; 3099
• 19a Fugami K, Morizawa Y, Oshima K, Nozaki H. Tetrahedron Lett. 1985; 26: 857
• 19b Fugami K, Miura K, Morizawa Y, Oshima K, Utimoto K, Nozaki H. Tetrahedron 1989; 45: 3089
• 20 Ohno H In Aziridines and Epoxides in Organic Synthesis . Yudin AK. Wiley-VCH; Weinheim, Germany: 2006: 37
• 21a Evans DA, Faul MM, Bilodeau MT. J. Org. Chem. 1991; 56: 6744
• 21b Carpino LA, Kirkley RK. J. Am. Chem. Soc. 1970; 92: 1784
• 21c Siu T, Yudin AK. J. Am. Chem. Soc. 2002; 124: 530
• 22 Jeong JU, Tao B, Sagasser I, Henniges H, Sharpless KB. J. Am. Chem. Soc. 1998; 120: 6844
• 23a Brichacek M, Lee D, Njardarson JT. Org. Lett. 2008; 10: 5023
• 23b For a review of 3-pyrroline synthetic approaches, see: Brichacek M, Njardarson JT. Org. Biomol. Chem. 2009; 7: 1761
• 24 Brichacek M, Batory LA, Njardarson JT. Angew. Chem. Int. Ed. 2010; 49: 1648
• 25 Corey EJ, Chaykovski M. J. Am. Chem. Soc. 1962; 84: 867
• 26 Darzens G. Compt. Rend. 1904; 139: 1214
• 27 For an example, see: Kang B, Britton R. Org. Lett. 2007; 9: 5083
• 28 Brichacek M, Villalobos MN, Plichta A, Njardarson JT. Org. Lett. 2011; 13: 1110
• 29a Liu G, Cogan DA, Ellman JA. J. Am. Chem. Soc. 1997; 119: 9913
• 29b Ellman JA, Owens TD, Tang TP. Acc. Chem. Res. 2002; 35: 984
• 29c Davis FA, Reddy RT, Reddy RE. J. Org. Chem. 1992; 57: 6387
• 29d Davis FA. J. Org. Chem. 2006; 71: 8993
• 30 Illa O, Arshad M, Ros A, McGarrigle EM, Aggarwal VK. J. Am. Chem. Soc. 2010; 132: 1828
• 31 For an example, see: Davis FA, Liu H, Zhou P, Fang T, Reddy GV, Zhang Y. J. Org. Chem. 1999; 64: 7559
• 32a Clard RD, Helmkamp GK. J. Org. Chem. 1964; 29: 1316
• 32b Muller RK, Felix D, Schreiber J, Eschenmosher A. Helv. Chim. Acta 1970; 53: 1479
• 33 Blakemore PR. J. Chem. Soc., Perkin Trans. 1 2002; 2563
• 34 Although the Aggarwal approach is a step shorter than Ellman’s for accessing chiral sulfonamides, it is worth noting that the sulfonamide imines needed are harder to make and far less stable than the sulfoxide imines, which are easily formed and readily purified by chromatography.
• 35 McGrath NA, Bartlett ES, Sittihan S, Njardarson JT. Angew. Chem. Int. Ed. 2009; 48: 8543
• 36 Wang J, Soisson SM, Young K, Shoop W, Kodali S, Galgoci A, Painter R, Parthasarathy G, Tang YS, Cummings R, Ha S, Dorso K, Motyl M, Jayasuriya H, Ondeyka J, Herath K, Zhang C, Hernandez L, Allocco J, Basilio A, Tormo JR, Genilloud O, Vicente F, Pelaez F, Colwell L, Lee SH, Michael B, Felcetto T, Gill C, Silver LL, Hermes JD, Bartizal K, Barrett J, Schmatz D, Becker JW, Cully D, Singh SB. Nature 2006; 441: 358
• 37a McGrath NA, Lee CA, Araki H, Brichacek M, Njardarson JT. Angew. Chem. Int. Ed. 2008; 47: 9450
• 37b Morton JG. M, Kwon LD, Freeman JD, Njardarson JT. Tetrahedron Lett. 2009; 50: 1684
• 37c Morton JG. M, Kwon LD, Freeman JD, Njardarson JT. Synlett 2009; 23
• 37d Morton JG. M, Dragichi C, Kwon LD, Njardarson JT. Org. Lett. 2009; 11: 4492
• 37e McGrath NA, Binner JR, Markopoulos G, Brichacek M, Njardarson JT. Chem. Commun. 2011; 47: 209
• 38 Molander GA, Petrillo DE. Org. Lett. 2008; 10: 1795
• 39 Li C, Pace EA, Liang M.-C, Lobkovsky E, Gilmore T, Porco JA. Jr. J. Am. Chem. Soc. 2001; 123: 11308
• 40 Gevorgyan V, Liu J.-X, Rubin M, Benson S, Yamamoto Y. Tetrahedron Lett. 1999; 40: 8919
• 41a Lalic G, Corey EJ. Org. Lett. 2007; 9: 4921
• 41b Tiefenbacher K, Mulzer J. Angew. Chem. Int. Ed. 2007; 46: 8074
• 42 Cao S.-G, Wu X.-H, Sim K.-Y, Tan BK. H, Pereira JT, Goh S.-H. Tetrahedron 1998; 54: 2143
• 43 Marigo M, Franzen J, Poulsen TB, Zhuang W, Jorgensen KE. J. Am. Chem. Soc. 2005; 127: 6964
• 44 Johnson WS, Werthemann L, Bartlett WR, Brocksom TJ, Li T.-T, Faulkner DJ, Petersen MR. J. Am. Chem. Soc. 1970; 92: 741
• 45 Gao Y, Sharpless KB. J. Am. Chem. Soc. 1988; 110: 7538
• 46 Malmstrom J, Christophersen C, Barrero AF, Oltra JE, Justicia J, Rosales A. J. Nat. Prod. 2002; 65: 364
• 47 Brichacek M, Batory LA, McGrath NA, Njardarson JT. Tetrahedron 2010; 66: 4832
• 48 For a Julia olefination example employing a similar sulfone, see: Esteban J, Costa AM, Vilarrasa J. Org. Lett. 2008; 10: 4843
• 49 Mack DJ, Njardarson JT. Angew. Chem. Int. Ed. 2013; 52: 1543
• 50a De Pascual Teresa J, San Feliciano A, Barrero AF. An. Quim. 1973; 69: 1065
• 50b Barrero AF, Herrador MM, Arteaga P, Arteaga JF, Arteaga AF. Molecules 2012; 17: 1448
• 51 Barrero AF, Rafael QM, Altarejos JC. Tetrahedron 1991; 47: 4441
• 52 Shi Y. Acc. Chem. Res. 2004; 37: 488
• 53 Nunez CV, Amendola MC, Henrique J, Lago G, Roque NF. Biochem. Sys. Eco. 2004; 32: 233
• 54a Iwamoto M, Ohtsu H, Tokuda H, Nishino H, Matsunaga S, Tanaka R. Bioorg. Med. Chem. 2001; 9: 1911
• 54b Li Y.-C, Kuo Y.-H. Chem. Pharm. Bull. 2002; 50: 498
• 54c Minami T, Iwamoto M, Ohtsu H, Ohishi H, Tanaka R, Yoshitake A. Planta Med. 2002; 68: 742
• 55 Wang Y.-Z, Tang C.-P, Ke C.-Q, Weiss H.-C, Gesing E.-R, Ye Y. Phytochemistry 2008; 69: 518
• 56 De Clercq PJ. Chem. Rev. 1997; 97: 1755
• 57 Ohrui H, Emoto S. Tetrahedron Lett. 1975; 2765
• 58 Herbert JM, Frehel D, Valee E, Kieffer G, Gouy D, Berger Y, Necciari J, Defreyn G, Maffrand JP. Cardiovasc. Drug Rev. 1993; 11: 180
• 59 Wohl A, Losanitsch MS. Ber. Dtsch. Chem. Ges. 1908; 40: 4685
• 60 Sadhu KM, Matteson DS. Tetrahedron Lett. 1986; 27: 795
• 61 Rossy PA, Hoffmann W, Muller N. J. Org. Chem. 1980; 45: 617
• 62 Carroll AR, Pierens GK, Fechner G, Leone PA, Ngo A, Simpson M, Hyde E, Hooper JN. A, Bostrom S.-L, Musil D, Quinn RJ. J. Am. Chem. Soc. 2002; 124: 13340
• 63 Mack DJ, Njardarson JT. Chem. Sci. 2012; 3: 3321
• 64a Pawlowski V, Kunkely H, Zabel M, Vogler A. Inorg. Chim. Acta 2004; 357: 824
• 64b Okazawa A, Ishida T, Nogami T. Polyhedron 2005; 24: 2584
• 64c Gurevich MZ, Sas TM, Mazepova ZV. V, Stepin BD. Zh. Neorg. Khim. 1975; 20: 735
• 65 Kitko DJ, Wiegers KE, Smith SG, Drago RS. J. Am. Chem. Soc. 1977; 99: 1410
• 66 Fukuyama T, Jow C.-K, Cheung M. Tetrahedron Lett. 1995; 36: 6373
• 67 For an example of cobaltocene being used to reduce copper(II) species to copper(I), see: Bond AM, Khalifa MA. Inorg. Chem. 1987; 26: 413
• 68 Jakubowski W, Matyjaszewski K. Macromolecules 2005; 38: 4139
• 69 Mahesh M, Murphy JA, LeStrat F, Wessel HP. Beilstein J. Org. Chem. 2009; 5: 1
• 70 Mustard TJ. L, Mack DJ, Njardarson JT, Cheong PH.-Y. J. Am. Chem. Soc. 2013; 135: 1471
• 71 Graddon DP, Ong WK. Aust. J. Chem. 1974; 27: 741
• 72 Rorabacher DB. Chem. Rev. 2004; 104: 651
• 73a Rutjes FP. J. T, Tjen KC. M, Wolf LB, Karstens WF. J, Schoemaker HE, Hiemstra H. Org. Lett. 1999; 1: 717
• 73b Wang C, Tunge JA. Org. Lett. 2006; 8: 3211
• 73c Dubovyk I, Pichugin D, Yudin AK. Angew. Chem. Int. Ed. 2011; 50: 5924
• 74 Guo B, Schwarzwalder G, Njardarson JT. Angew. Chem. Int. Ed. 2012; 51: 5675
• 75a Evans DA, Woerpel KA, Hinman MM, Faul MM. J. Am. Chem. Soc. 1991; 113: 726
• 75b Corey EJ, Imai N, Zhang H.-Y. J. Am. Chem. Soc. 1991; 113: 728
• 76a Akiyama T. Chem. Rev. 2007; 107: 5744
• 76b Rueping M, Nachtsheim BJ, Leawsuwan W, Atodiresei I. Angew. Chem. Int. Ed. 2011; 50: 2
• 76c Rueping M, Uria U, Lin M.-Y, Atodieresei I. J. Am. Chem. Soc. 2011; 133: 3732
• 77a Akiyama T, Itoh J, Yokota K, Fuchibe K. Angew. Chem. Int. Ed. 2004; 43: 1566
• 77b Nakashima D, Yamamoto H. J. Am. Chem. Soc. 2006; 128: 9626