Synthesis of γ,δ-Unsaturated Selenoamides via the Seleno-Claisen Rearrangement of in situ Generated Allylic Vinyl Selenides from Selenoamides and Allylic Bromides­

Abstract

The deprotonation of α-monosubstituted selenoamides with LDA followed by allylation gives γ,δ-unsaturated selenoamides in good to high yields. In the initial step, allylation may take place at the selenium atom of lithium eneselenolates to form allylic vinyl selenides, which then undergo seleno-Claisen rearrangement. As allylic bromides, γ,γ-disubstituted compounds such as geranyl and neryl bromides could also be used to give products that incorporated tertiary-quaternary stereogenicity with high efficiency.

Key words

seleno-Claisen rearrangement - γ,δ-unsaturated selenoamides - tertiary-quaternary stereogenicity - high stereoselectivity

• References


For recent reviews, see:
• 1a Claisen Rearrangement . Hiersemann M, Nubbemeyer U. Wiley-VCH; Weinheim: 2007
• 1b Tymoshenko DO. Mini-Rev. Org. Chem. 2008; 5: 85
• 1c Hiratani K, Albrecht M. Chem. Soc. Rev. 2008; 37: 2413
• 1d White JD, Yang J. Synlett 2009; 1713
• 1e Pinto MM. M, Castanheiro RA. P. Curr. Org. Chem. 2009; 13: 1215
• 1f Hewlett NM, Hupp CD, Tepe JJ. Synthesis 2009; 2825
• 1g Kotha S, Krishna NG, Halder S, Misra S. Org. Biomol. Chem. 2011; 9: 5597
• 1h Davies HM. L, Yajing L. Acc. Chem. Res. 2012; 45: 923
• 1i Liu Z, Metha SJ, Hruby VJ. Org. Prep. Proced. Int. 2012; 44: 222
• 2 For a review, see: Fernandez de la Pradilla R, Tortosa M, Viso A. In Topics in Current Chemistry . Vol. 275. Schaumann E. Springer Verlag; Berlin: 2007: 103

For recent examples, see:
• 3a Liu Z, Qu H, Gu X, Min BJ, Nyberg J, Hruby VJ. Org. Lett. 2008; 10: 4105
• 3b Majumdar KC, Alam S, Chattopadhyay B. J. Heterocycl. Chem. 2009; 46: 62
• 3c Zhou H, Xie YF, Ren L.-J, Su R. Org. Lett. 2010; 12: 356
• 3d Sabahi A, Rainer JD. ARKIVOC 2010; (viii): 116
• 3e Liu Z, Qu H, Gu X, Lee K.-S, Grossman B, Kumirov VK, Hruby VJ. Tetrahedron Lett. 2010; 51: 3518
• 3f Zahedi E, Shiroudi A, Ali-Asgari S, Keley V. Phosphorus, Sulfur Silicon Relat. Elem. 2011; 186: 159
• 3g Majumdar KC, Nath S, Chattopadhyay B, Ray K. Lett. Org. Chem. 2011; 8: 176
• 3h Liu Z, Mehya SJ, Lee K.-S, Grossman B, Qu H, Gu X, Nichol GS, Hruby VJ. J. Org. Chem. 2012; 77: 1289
• 3i Jiang B, Han L, Li Y.-L, Zhao X.-L, Lei Y, Xie D.-Q, Zhang JZ. H. J. Org. Chem. 2012; 77: 1701
• 4a Yannick V, Mark W. Chem. Commun. 1992; 1680
• 4b Kato S, Komuro T, Kanda T, Ishihara H, Murai T. J. Am. Chem. Soc. 1993; 115: 3000
• 4c Shimada K, Oikawa S, Nakamura H, Takikawa Y. Chem. Lett. 1995; 135
• 4d Brandsma L, Morkved EH, Bjorio O, Potapov VA, Amosova SV. Sulfur Lett. 2000; 23: 215
• 4e Prabhakar S, Mirza SP, Kundu A, Roy S, Vairamani M. Rapid Commun. Mass Spectrom. 2000; 14: 1116
• 4f Stefani HA, Petragnani N, Ascenso MF. C, Zeni G. Synth. Commun. 2003; 33: 2161
• 4g Kumar S, Johansson H, Engman L, Valgimigli L, Amorati R, Fumo MG. J. Org. Chem. 2007; 72: 2583
• 5a Murai T, Takada H, Kanda T, Kato S. Chem. Lett. 1995; 1057
• 5b Murai T, Takada H, Kakami K, Fujii M, Maeda M, Kato S. Tetrahedron 1997; 53: 12237
• 6 Gompper R, Kohl B. Tetrahedron Lett. 1980; 21: 917
• 7 Castro AM. M. Chem. Rev. 2004; 104: 2939

For reviews of selenoamides, see:
• 8a Murai T In Topics in Current Chemistry . Vol. 251. Kato S. Springer Verlag; Berlin: 2005: 247
• 8b Koketsu M, Ishihara H. Curr. Org. Synth. 2007; 4: 15
• 8c Murai T In Organoselenium Chemistry . Wirth T. Wiley-VCH; Weinheim: 2012: 257

For preparation of selenoamides, see:
• 9a Li GM, Zingaro RA. J. Chem. Soc., Perkin Trans. 1 1998; 647
• 9b Murai T, Ezaka T, Kato S. Bull. Chem. Soc. Jpn. 1998; 71: 1193
• 9c Ishihara H, Yosimura K, Kouketsu M. Chem. Lett. 1998; 1287
• 9d Bhattacharyya P, Woollins JD. Tetrahedron Lett. 2001; 42: 5949
• 9e Ishihara H, Koketsu M, Fukuta Y, Nada F. J. Am. Chem. Soc. 2001; 123: 8408
• 9f Koketsu M, Okayama Y, Aoki H, Ishihara H. Heteroat. Chem. 2002; 13: 195
• 9g Bethke J, Karaghiosoff K, Wessjohann LA. Tetrahedron Lett. 2003; 44: 6911
• 9h Saravanan V, Mukherjee C, Das S, Chandrasekaran S. Tetrahedron Lett. 2004; 45: 681
• 9i Hua G, Li Y, Slawin AM. Z, Woollins JD. Org. Lett. 2006; 8: 5251
• 9j Hua G, Woollins JD. Angew. Chem. Int. Ed. 2009; 48: 1368
• 9k Shibahara F, Sugiura R, Murai T. Org. Lett. 2009; 11: 3064

For lithium eneselenolates derived from selenoamides, see:
• 10a Murai T, Ezaka T, Ichimiya T, Kato S. Synlett 1997; 775
• 10b Murai T, Suzuki A, Ezaka T, Kato S. Org. Lett. 2000; 2: 311
• 10c Murai T, Suzuki A, Kato S. Phosphorus, Sulfur Silicon Relat. Elem. 2001; 171-172: 355
• 10d Murai T, Suzuki A, Kato S. J. Chem. Soc., Perkin Trans. 1 2001; 2711
• 10e Murai T, Ishizuka M, Suzuki A, Kato S. Tetrahedron Lett. 2003; 44: 1343
• 10f Murai T, Fujishima A, Iwamoto C, Kato S. J. Org. Chem. 2003; 68: 7979
• 11a Murai T, Kakami K, Itoh N, Kanda T, Kato S. Tetrahedron 1996; 52: 2839
• 11b Murai T, Endo H, Ozaki M, Kato S. J. Org. Chem. 1999; 64: 2130
• 11c Murai T, Hayakawa S, Kato S. J. Org. Chem. 2001; 66: 8101
• 12a Tamaru Y, Harada Y, Nishi S, Mizutani M, Hioki T, Yoshida Z. J. Am. Chem. Soc. 1980; 102: 7808
• 12b Sergey SH, Kozmin SA, Rawal VH. J. Am. Chem. Soc. 2000; 122: 190

For examples of compounds having similar carbon skeletons, see:
• 13a Lambert TH, MacMillan DW. C. J. Am. Chem. Soc. 2002; 124: 13646
• 13b Temmem O, Uguen D, Cian AD, Gruber N. Tetrahedron Lett. 2002; 43: 3169

For recent examples for the construction of consecutive tertiary-quaternary carbon stereocenters, see:
• 14a Qin Y.-c, Stivala CE, Zakarian A. Angew. Chem. Int. Ed. 2007; 46: 7466
• 14b Fleming FF, Liu W, Ghosh S, Steward OW. Angew. Chem. Int. Ed. 2007; 46: 7098
• 14c Kawatsura M, Ikeda D, Komatsu Y, Mitani K, Tanaka T, Uenishi J. Tetrahedron 2007; 63: 8815
• 14d Uyeda C, Jacobsen EN. J. Am. Chem. Soc. 2008; 130: 9228
• 14e Fleming FF, Liu W, Ghosh S, Steward OW. J. Org. Chem. 2008; 73: 2803
• 14f Wang H, Tassa C, Jacobi PA. Org. Lett. 2008; 10: 2837
• 14g Sugiyama S, Nakata N, Satoh T. Tetrahedron: Asymmetry 2008; 19: 401
• 14h Stivala CE, Zakarian A. Org. Lett. 2009; 11: 839
• 14i Kitamoto K, Sampei M, Nakayama Y, Sato T, Chida N. Org. Lett. 2010; 12: 5756
• 14j Schwartz KD, White JD. Org. Lett. 2011; 13: 248
• 14k Zhuang Z, Chen J.-M, Feng P, Liao W.-W. Org. Lett. 2012; 14: 2354

For carbon–carbon bond-forming reactions using selenoamides, see:
• 15a Murai T, Ezaka T, Kato S. Tetrahedron Lett. 1998; 39: 4329
• 15b Murai T, Mutoh Y, Kato S. Org. Lett. 2001; 3: 1993
• 15c Mutoh Y, Murai T. Org. Lett. 2003; 5: 1361
• 15d Murai T, Nogawa S, Mutoh Y. Bull. Chem. Soc. Jpn. 2007; 80: 2220
• 15e Hussaini SR, Hammond GB. ARKIVOC 2008; (xiii): 129
• 15f Mitamura T, Nomoto A, Sonoda M, Ogawa A. Tetrahedron 2008; 64: 9983
• 15g Mitamura T, Ogawa A. Org. Lett. 2009; 11: 2045
• 16 Sugiura M, Nakai T. Chem. Lett. 1995; 697