Crossing the Ring: A Journey of the Nitroso-ene Reaction

Abstract

Recent progress in the nitroso-ene reaction indicates the potentially rich reactivity of the nitroso species. In this study, we highlight the synthetic efforts towards the construction of the aza-spirocyclic or aza-bridged ring embedded in biologically significant alkaloids via the proposed approach. Our endeavors along this direction are exemplified in the formal synthesis of (±)-cephalotaxine and the total synthesis of (–)-hosieine A.

1 Introduction

2 Aza-Spirocyclane: A Formal Synthesis of (±)-Cephalotaxine

3 Method Development

4 Aza-Bridge Ring: A Total Synthesis of (–)-Hosieine A

5 Epilogue

Keywords

alkaloids - alkene functionalization - mechanism - nitroso-ene reaction - total synthesis

• References

• 1 Fattorusso E, Taglialatela-Scafati O. Modern Alkaloids . Wiley-VCH; Weinheim: 2008
• 2 Bariwal J, Van der Eycken E. Chem. Soc. Rev. 2013; 42: 9283

For reviews see:
• 3a Ager DJ, Prakash I, Schaad DR. Chem. Rev. 1996; 96: 835
• 3b Lait SM, Rankic DA, Keay BA. Chem. Rev. 2007; 107: 767

Reviews on nitroso-ene reactions see:
• 4a Adam W, Krebs O. Chem. Rev. 2003; 103: 4131
• 4b Huang S.-H, Huo H, Li W, Hong R. Chin. J. Org. Chem. 2012; 32: 1776
• 4c Baidya M, Yamamoto H. Synthesis 2013; 45: 1931
• 4d Palmer LI, Frazier CP, Read de Alaniz J. Synthesis 2014; 46: 269
• 5a Meyer V, Locher J. Ber. Dtsch. Chem. Ges. 1874; 7: 670
• 5b Meyer V, Locher J. Ber. Dtsch. Chem. Ges. 1874; 7: 1506
• 5c Baeyer A, Caro H. Ber. Dtsch. Chem. Ges. 1874; 7: 809
• 5d Baeyer A. Ber. Dtsch. Chem. Ges. 1874; 7: 1638
• 5e Baeyer A, Caro H. Ber. Dtsch. Chem. Ges. 1874; 7: 963
• 6a Kirby GW. Chem. Soc. Rev. 1977; 6: 12
• 6b Kirby GW, Sweeny JG. J. Chem. Soc., Perkin Trans. 1 1981; 3250
• 6c Corrie JE. T, Kirby GW, Sharma RP. J. Chem. Soc., Perkin Trans. 1 1982; 1571
• 6d Corrie JE. T, Kirby GW. J. Chem. Soc., Perkin Trans. 1 1985; 881
• 6e Kirby GW, Mackinnon JW. M. J. Chem. Soc., Perkin Trans. 1 1985; 887
• 6f Kirby GW, McGuigan H, Mackinnon JW. M. J. Chem. Soc., Perkin Trans. 1 1985; 1437
• 6g Kirby GW, McGuigan H, McLean D. J. Chem. Soc., Perkin Trans. 1 1985; 1961
• 7 Keck GE, Webb RR, Yates JB. Tetrahedron 1981; 37: 4007
• 8 Malkov AV, Atkinson D, Kabeshov MA, Edgar MA. Adv. Synth. Catal. 2011; 353: 3347
• 9 Adam W, Bottke N, Krebs O, Saha-Moèller CR. Eur. J. Org. Chem. 1999; 1963
• 10a Chaiyaveij D, Cleary L, Batsanov AS, Marder TB, Shea KJ, Whiting A. Org. Lett. 2011; 13: 3442
• 10b Frazier CP, Engelking JR, Read de Alaniz J. J. Am. Chem. Soc. 2011; 133: 10430

For early studies on the nitroso-ene reaction, see:
• 11a Alessandri L, Angeli A, Pegna R. Atti. accud. Lincei 1910; 19: 650
• 11b Alessandri L. Atti. accud. Lincei. 1915; 24: 62
• 11c Alessandti L. Gazz. Chim. Ital. 1921; 51: 129
• 11d Bruni G, Gieger E. Rubber Chem. and Tech. 1928; 1: 177
• 11e Pummer R, Giindel W. Rubber Chem. and Tech. 1929; 2: 373
• 11f Banks RE, Barlow MG, Haszeldine RN. J. Chem. Soc. 1965; 4714
• 11g Knight GT, Pepper B. Tetrahedron 1971; 27: 6201
• 12a Keck GE, Webb RR. J. Am. Chem. Soc. 1981; 103: 3173
• 12b Keck GE, Webb RR. J. Org. Chem. 1982; 47: 1302
• 12c Keck GE, Webb RR. J. Org. Chem. 1982; 47: 1302
• 13 Maji B, Yamamoto H. J. Am. Chem. Soc. 2015; 137: 15957
• 14a Wan KK, Iwasaki K, Umotoy JC, Wolan DW, Shenvi RA. Angew. Chem. Int. Ed. 2015; 54: 2410

For a recent account, see:
• 14b Wan KK, Shenvi RA. Synlett 2016; 27: 1145
• 15a Paudlar WW, Kerley GI, Mckay J. J. Org. Chem. 1963; 28: 2194
• 15b Arora SK, Bates RB, Grady RA, Powell RG. J. Org. Chem. 1974; 39: 1269
• 16a Kuramoto M, Tong C, Yamada K, Chiba T, Hayashi Y, Uemura D. Tetrahedron Lett. 1996; 37: 3867
• 16b Arimoto H, Hayakawa I, Kuramoto M, Uemura D. Tetrahedron Lett. 1998; 39: 861
• 17 Sakamoto K, Tsujii E, Abe F, Nakanishi T, Yamashita M, Shigematsu N, Izumi S, Okuhara M. J. Antibiot. 1996; 49: 37
• 18a Liu H, Yu J, Li X, Yan R, Xiao J.-C, Hong R. Org. Lett. 2015; 17: 4444

See our early efforts on the construction of azepine using the iminium ion approach:
• 18b Li C, Li X, Hong R. Org. Lett. 2009; 11: 4036
• 18c Wang Y, Zhu L, Zhang Y, Hong R. Angew. Chem. Int. Ed. 2011; 50: 2787
• 18d Mi X, Wang Y, Zhu L, Wang R, Hong R. Synthesis 2012; 44: 3432

Reviews:
• 19a Huang L, Xue Z In The Alkaloids: Chemistry and Pharmacology . Vol. 23. Brossi A. Academic Press; New York: 1984: 157
• 19b Hudlicky T, Kwart LD, Reed JW In The Alkaloids: Chemical and Biological Perspectives . Vol. 5. Pelletier SW. John Wiley and Sons; New York: 1987: 639
• 19c Jalil Miah MA, Hudlicky T, Reed JW In The Alkaloids: Chemistry and Biology . Vol. 51. Brossi A. Academic Press; New York: 1998: 199
• 19d Abdebafi H, Nay B. Nat. Prod. Rep. 2012; 29: 845
• 20 Matsumura Y, Aoyagi S, Kibayashi C. Org. Lett. 2003; 5: 3249
• 21 Huang S.-H, Tian X.-C, Mi X, Wang Y, Hong R. Tetrahedron Lett. 2015; 56: 6656
• 22 Tietze LF, Schirok H. Angew. Chem. Int. Ed. 1997; 36: 1124
• 23 Chou T, Kuramoto M, Otani Y, Shikano M, Yazawa K, Uemura D. Tetrahedron Lett. 1996; 37: 3871
• 24 Trauner D, Schwarz JB, Danishefsky SJ. Angew. Chem. Int. Ed. 1999; 38: 3542

Review:
• 25a Clive DL. J, Yu ML, Wang J, Yeh VS. C, Kang SZ. Chem. Rev. 2005; 105: 4483

For recent examples, see:
• 25b Wu H, Zhang HG, Zhao G. Tetrahedron 2007; 63: 6454
• 25c Xu S, Arimoto H, Uemura D. Angew. Chem. Int. Ed. 2007; 46: 5746
• 26a Matsumura Y, Aoyagi S, Kibayashi C. Org. Lett. 2003; 5: 3249
• 26b Matsumura Y, Aoyagi S, Kibayashi C. Org. Lett. 2004; 6: 965
• 27 Knapp S, Levorse AT. J. Org. Chem. 1998; 53: 4006
• 28 Mi XW. Part II. Aza-heterocycles using nitroso-ene reaction. Ph.D. Dissertation. Shanghai Institute of Organic Chemistry; Shanghai: 2015
• 29a Ameri A. Prog. Neurobiol. 1998; 56: 211
• 29b Dobelis P, Madl JE, Pfister JA, Manners GD, Walrond JP. J. Pharmacol. Exp. Ther. 1999; 291: 538
• 30a Saito K, Murakoshi I In Studies in Natural Products Chemistry Structure and Chemistry (Part C) . Vol. 15. Rahman AU. Elsevier; Amsterdam: 1995: 519
• 30b Bunsupa S, Yamazaki M, Saito K. Front. Plant Sci. 2012; 3: 239
• 31 Pouny I, Batut M, Vendier L, David B, Yi S, Sautel F, Arimondo PB, Massiot G. Phytochemistry 2014; 107: 97
• 32a Gotti C, Clementi F. Prog. Neurobiol. 2004; 74: 363
• 32b Morten G, Grunnet M, Bastlund JF, Jensen AA. Basic Clin. Pharmacol. Toxicol. 2015; 116: 187
• 33a Pérez EG, Méndez-Gálvez C, Cassels BK. Nat. Prod. Rep. 2012; 29: 555
• 33b Rouden J, Lasne M.-C, Blanchet J, Baudoux J. Chem. Rev. 2014; 114: 712
• 34 Desai P, Schildknegt K, Agrios KA, Mossman C, Milligan GL, Aubé J. J. Am. Chem. Soc. 2000; 122: 7226
• 35 Bultman MS, Ma J, Gin DY. Angew. Chem. Int. Ed. 2008; 47: 6821
• 36a Gray D, Gallagher T. Angew. Chem. Int. Ed. 2006; 45: 2419
• 36b Gallagher T, Derrick I, Durkin PM, Haseler CA, Hirschhäuser C, Magrone P. J. Org. Chem. 2010; 75: 3766
• 36c Durkin PM, Magrone P, Matthews S, Dallanoce C, Gallagher T. Synlett 2010; 2789
• 37 Ouyang J, Yan R, Mi XW, Hong R. Angew. Chem. Int. Ed. 2015; 54: 10940
• 38a Lentsch C, Rinner U. Org. Lett. 2009; 11: 5362
• 38b Meiries S, Bartoli A, Decostanzi M, Parrain J.-L, Commmeiras L. Org. Biomol. Chem. 2013; 11: 4882
• 39a Blanchette MA, Choy W, Davis JT, Essenfeld AP, Masamune S, Roush WR, Sakai T. Tetrahedron Lett. 1984; 25: 2183
• 39b Li S.-G, Jin J.-W, Wu Y. Tetrahedron 2012; 68: 846
• 40 Adam W, Bottke N, Krebs O, Saha-Möller CR. Eur. J. Org. Chem. 1999; 1963
• 41 Leach AG, Houk KN. J. Am. Chem. Soc. 2002; 124: 14820
• 42 Mattingly PG, Miller MJ. J. Org. Chem. 1980; 45: 410
• 43a Anderl PT, Emo M, Laschat S, Baro A, Frey W. Synthesis 2008; 1619
• 43b Clay JM, Vedejs E. J. Am. Chem. Soc. 2005; 127: 5766
• 43c Evans DA, Fu GC, Hoveyda AH. J. Am. Chem. Soc. 1992; 114
• 43d Harding KE, Marman TH. J. Org. Chem. 1984; 49: 2838
• 44 Hashimoto N, Kanda A. Org. Proc. Res. Dev. 2002; 6: 405
• 45 Barrero AF, Quílez del Moral JF, Sánchez EM, Arteaga JF. Eur. J. Org. Chem. 2006; 1627
• 46 Hanessian S, Jennequin T, Boyer N, Babonneau V, Soma U, la Cour CM, Millan MJ, De Nanteuil G. ACS Med. Chem. Lett. 2014; 5: 550
• 47a Adimurthy S, Ghosh S, Patoliya PU, Ramachandraiah G, Agrawal M, Gandhi MR, Upadhyay SC, Ghosh PK, Ranu BC. Green Chem. 2008; 10: 232
• 47b Podgoršek A, Zupan M, Iskra J. Angew. Chem. Int. Ed. 2009; 48: 8424
• 48 Paddon-Row MN, Wu YD, Houk KN. J. Am. Chem. Soc. 1992; 114: 10638
• 49a Sakakura A, Ukai A, Ishihara K. Nature 2007; 445: 900
• 49b Sakakura A, Shomi G, Ukai A, Ishihara K. Heterocycles 2011; 82: 249
• 49c Sawamura Y, Nakatsuji H, Sakakura A, Ishihara K. Chem. Sci. 2003; 4: 4181
• 49d Sawamura Y, Nakatsuji H, Akakura M, Sakakura A, Ishihara K. Chirality 2014; 26: 356
• 49e Sakakura A, Ishihara K. Chem. Rec. 2015; 15: 728
• 50 Personal communications with Professor Timothy C. Gallagher.