Isocyanide-Based Multicomponent Reactions: Rapid Synthesis of a 5,5-Fused Bicyclic Skeleton from α,β-Unsaturated Ketones and Allenoates

Abstract

An efficient multicomponent reaction of isocyanides, allenoates, and α,β-unsaturated ketones is disclosed, thus providing rapid access for the synthesis of bicyclic skeletons. From a mechanistic standpoint, the present cycloaddition proceeds through cascade cycloaddition followed by hydration and intramolecular cyclization. Several controlled experiments are also conducted to gain further insight into the reaction mechanism; some valuable and interesting findings were observed during this process. To enrich the structural diversity, 3-(2-oxo­ethylene)indolinones (i.e. with an α,β-unsaturated ketone at position 3) were also found to be compatible in this reaction. In addition, this method is also characterized by its broad substrate scope, mild conditions, and high efficiency, which makes it valuable for further application.

Key words

isocyanide - multicomponent reaction - allenoate - bicyclic skeleton - α,β-unsaturated ketone

• References

• 1 S.X. and S.S. contributed equally to this work.

For recent examples, see:
• 2a Buyck T, Wang Q, Zhu J. J. Am. Chem. Soc. 2014; 136: 11524
• 2b Mampuys P, Zhu Y, Vlaar T, Ruijter E, Orru RV. A, Maes BU. W. Angew. Chem. Int. Ed. 2014; 53: 12849
• 2c Kakuchi R. Angew. Chem. Int. Ed. 2014; 53: 46
• 2d Buyck T, Wang Q, Zhu J. Angew. Chem. Int. Ed. 2013; 52: 12714
• 2e Lei C.-H, Wang D.-X, Zhao L, Zhu J, Wang M.-X. J. Am. Chem. Soc. 2013; 135: 4708
• 2f Zajdlik A, Wang Z, Hickey JL, Aman A, Schimmer AD, Yudin AK. Angew. Chem. Int. Ed. 2013; 52: 8411
• 2g Qiu G, Ding Q, Wu J. Chem. Soc. Rev. 2013; 42: 5257
• 2h Okitsu T, Nagase K, Nishio N, Wada A. Org. Lett. 2012; 14: 708

For construction of heterocycles, see: Indole:
• 3a Liu J, Liu Z, Liao P, Bi X. Org. Lett. 2014; 16: 6204
• 3b Nanjo T, Tsukano C, Takemoto Y. Org. Lett. 2012; 14: 4270

For a review on synthesis of indoles from isocyanides, see:
• 3c Campo J, Garcia-Valverde M, Marcaccini S, Rojo M, Torroba JT. Org. Biomol. Chem. 2006; 4: 757

Oxazole:
• 3d Janvier P, Bois-Choussy M, Bienaymé H, Zhu J. Angew. Chem. Int. Ed. 2003; 42: 811
• 3e Larionov OV, de Meijere A. Angew. Chem. Int. Ed. 2005; 44: 5664
• 3f Lygin AV, Larionov OV, Korotkov VS, de Meijere A. Chem. Eur. J. 2009; 15: 227

Imidazole:
• 3g Helal CJ, Lucas JC. Org. Lett. 2002; 4: 4133
• 3h Kanazawa C, Kamijo S, Yamamoto Y. J. Am. Chem. Soc. 2006; 128: 10662
• 3i van Leusen AM, Wildeman J, Oldenyiel OH. J. Org. Chem. 1977; 42: 1153

For the synthesis of other rings, see:
• 3j Liu J, Fang Z, Zhang Q, Liu Q, Bi X. Angew. Chem. Int. Ed. 2013; 52: 6953
• 3k Vlaar T, Mampuys P, Helliwell M, Maes BU. W, Orru RV. A, Ruijter E. J. Org. Chem. 2013; 78: 6735
• 3l Qiu G, He Y, Wu J. Chem. Commun. 2012; 48: 3836

For palladium-catalyzed insertion of isocyanide, see:
• 4a Vlaar T, Ruijter E, Maes BU. W, Orru RV. A. Angew. Chem. Int. Ed. 2013; 52: 7084
• 4b Baelen GV, Kuijer S, Rýcěk L, Sergeyev S, Janssen E, de Kanter FJ. J, Maes BU. W, Ruijter E, Orru RV. A. Chem. Eur. J. 2011; 17: 15039
• 4c Tobisu M, Imoto S, Ito S, Chatani N. J. Org. Chem. 2010; 75: 4835

For other metal-catalyzed insertion, see:
• 4d Zhang M, Buchwald SL. J. Org. Chem. 1996; 61: 4498
• 4e Jones WD, Kosar WP. J. Am. Chem. Soc. 1986; 108: 5640

For radical based examples, see:
• 5a Jiang H, Cheng Y, Wang R, Zhang Y, Yu S. Chem. Commun. 2014; 50: 6164
• 5b Jiang H, Cheng Y, Wang R, Zheng M, Zhang Y, Yu S. Angew. Chem. Int. Ed. 2013; 52: 13289
• 5c Tobisu M, Koh K, Furukawa T, Chatani N. Angew. Chem. Int. Ed. 2012; 51: 11363
• 5d Mitamura T, Iwata K, Ogawa A. J. Org. Chem. 2011; 76: 3880
• 5e Sumi S, Matsumoto K, Tokuyama H, Fukuyama T. Org. Lett. 2003; 5: 1891
• 5f Curran DP, Liu H. J. Am. Chem. Soc. 1992; 114: 5863
• 5g Curran DP, Liu H. J. Am. Chem. Soc. 1991; 113: 2127
• 6 This unique property is also shared with carbon monoxide and formally divalent carbenes.
• 7a Multicomponent Reactions in Organic Synthesis . Zhu J, Wang Q, Wang M.-X. Wiley-VCH; Weinheim: 2014
• 7b Ruijter E, Scheffelaar R, Orru RV. A. Angew. Chem. Int. Ed. 2011; 50: 6234
• 7c Toure BB, Hall DG. Chem. Rev. 2009; 109: 4439
• 7d Sunderhaus JD, Martin SF. Chem. Eur. J. 2009; 15: 1300
• 7e Isambert N, Lavilla R. Chem. Eur. J. 2008; 14: 8444
• 7f Dömling A. Chem. Rev. 2006; 106: 17
• 7g Ramón DJ, Yus M. Angew. Chem. Int. Ed. 2005; 44: 1602

For atom economy:
• 8a Trost BM. Science (Washington, D.C.) 1991; 254: 1471

For step economy:
• 8b Wender PA, Verma VA, Paxton TJ, Pillow TH. Acc. Chem. Res. 2008; 41: 40

For redox economy:
• 8c Richter JM, Ishihara Y, Masuda T, Whitefield BW, Llamas T, Pohjakallio A, Baran PS. J. Am. Chem. Soc. 2008; 130: 17938
• 9a Wang X, Wang S.-Y, Ji S.-J. Org. Lett. 2013; 15: 1954
• 9b Santra S, Andreana PR. Angew. Chem. Int. Ed. 2011; 50: 9418
• 9c Riva R, Banfi L, Basso A, Cerulli V, Guanti G, Pani M. J. Org. Chem. 2010; 75: 5134
• 9d Znabet A, Zonneveld J, Janssen E, De Kanter FJ. J, Helliwell M, Turner NJ, Ruijter E, Orru RV. A. Chem. Commun. 2010; 46: 7706
• 9e Janvier P, Bienaymé H, Zhu J. Angew. Chem. Int. Ed. 2002; 41: 4291
• 10a Solleder SC, Meier MA. R. Angew. Chem. Int. Ed. 2014; 53: 711
• 10b Lei C.-H, Zhao L, Wang D.-X, Zhu J, Wang M.-X. Org. Chem. Front. 2014; 1: 909
• 10c Basavanag UM. V, Santos AD, El Kaim L, Gámez-Montaño R, Grimaud L. Angew. Chem. Int. Ed. 2013; 52: 7194
• 10d Wang X, Xu X.-P, Wang S.-Y, Zhou W, Ji S.-J. Org. Lett. 2013; 15: 4246
• 10e Qiu G, Liu G, Pu SZ, Wu J. Chem. Commun. 2012; 48: 2903
• 11 Li J, Liu YJ, Li CJ, Jia XS. Chem. Eur. J. 2011; 17: 7409
• 12a Li J, Liu YJ, Li CJ, Jia XS. Adv. Synth. Catal. 2011; 353: 913
• 12b Li J, Wang N, Li CJ, Jia XS. Chem. Eur. J. 2012; 18: 9645
• 12c Su SK, Li CJ, Jia XS, Li J. Chem. Eur. J. 2014; 20: 5905
• 12d Jia SL, Su SK, Li CJ, Jia XS, Li J. Org. Lett. 2014; 16: 5604
• 13 CCDC 1041737 for compound 5d contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
• 14 CCDC 1041829 for compound 6l contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
• 15a Xing Y, Cheng B, Wang J, Lu P, Wang Y. Org. Lett. 2014; 16: 4814
• 15b Sun L, Zhu Y, Lu P, Wang Y. Org. Lett. 2013; 15: 5894
• 15c Li H, Hsung RP, DeKorver KA, Wei Y. Org. Lett. 2010; 12: 3780
• 16a Jiang HF, Liu BF, Li YB, Wang AZ, Huang HW. Org. Lett. 2011; 13: 1028
• 16b Shaabani A, Maleki A, Mofakham H, Moghimi-Rad J. J. Org. Chem. 2008; 73: 3925

For reviews, see:
• 17a Zhou F, Liu Y.-L, Zhou J. Adv. Synth. Catal. 2010; 352: 1381
• 17b Galliford CV, Scheidt KA. Angew. Chem. Int. Ed. 2007; 46: 8748
• 17c Trost BM, Jiang C. Synthesis 2006; 369
• 17d Williams RM, Cox RJ. Acc. Chem. Res. 2003; 36: 127
• 17e Marti C, Carreira EM. Eur. J. Org. Chem. 2003; 2209
• 18a Kotha S, Deb AC, Lahiri K, Manivannan E. Synthesis 2009; 165
• 18b Greshock TJ, Grubbs AW, Jiao P, Wicklow DT, Gloer JB, Williams RM. Angew. Chem. Int. Ed. 2008; 47: 3573
• 18c Lo MM.-C, Neumann CS, Nagayama S, Perlstein EO, Schreiber SL. J. Am. Chem. Soc. 2004; 126: 16077
• 18d Venkatesan H, Davis MC, Altas Y, Snyder D, Liotta C. J. Org. Chem. 2001; 66: 3653
• 19 CCDC 1041914 for compound 8a contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
• 20 Tan B, Candeias NR, Barbas CF. III. Nat. Chem. 2011; 3: 473
• 21 CCDC 1041830 for compound 9a contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.

The first step is also a formal [3+2] cycloaddition, which is similar to phosphine-catalyzed [3+2] cycloaddition with allenoate. Please see:
• 22a Liang Y, Liu S, Xia Y, Li Y, Yu Z. Chem.–Eur. J. 2008; 14: 4361
• 22b Xia Y, Liang Y, Chen Y, Wang M, Jiao L, Huang F, Liu S, Li Y, Yu Z. J. Am. Chem. Soc. 2007; 129: 3470
• 22c Zhang C, Lu X. J. Org. Chem. 1995; 60: 2906
• 23 Substituted allenoate also serves as C4 component in phosphine-catalyzed [4+2] cycloaddition by using one carbon atom in alkyl substituent for the ring formation, which is different from the present multicomponent reaction.
• 24a Ugi I, Meyr R. Org. Synth. Coll. Vol. V . John Wiley & Sons; London: 1973
• 24b Obrecht R, Herrmann R, Ugi I. Synthesis 1985; 400
• 25a Creech GS, Kwon O. Org. Lett. 2008; 10: 429
• 25b Zhu X.-F, Lan J, Kwon O. J. Am. Chem. Soc. 2003; 125: 4716
• 26 Ding B.-Q, Zhang Z.-F, Liu Y.-G, Sugiya M, Imamoto T, Zhang W.-B. Org. Lett. 2013; 15: 3690
• 27a Trost BM, Zhang Y. J. Am. Chem. Soc. 2007; 129: 14548
• 27b Shintani R, Inoue M, Hayashi T. Angew. Chem. Int. Ed. 2006; 45: 3353
• 27c Lindwall HG, Maclennan JS. J. Am. Chem. Soc. 1932; 54: 4739
• 28a Marti C, Carreira EM. J. Am. Chem. Soc. 2005; 127: 11505
• 28b Ellis JM, Overman LE, Tanner HR, Wang J. J. Org. Chem. 2008; 73: 9151