Asymmetric N-Heterocyclic Carbene-catalyzed [4+2] Cycloaddition of Ketenes with α-cyanochalcones

doi:10.6023/A14040334

Abstract

The N-heterocyclic carbene (NHC)-catalyzed enantioselective cycloaddition reactions of ketenes are powerful methods for the synthesis of chiral heterocycles. Followed by the previous reported NHC-catalyzed [2+2] and [4+2] cycloaddtion of ketenes with imines, ketones and various heterodienes, the NHC-catalyzed enantioselective [4+2] cycloaddition of ketenes with α-cyanochalcones was investigated in this paper. In the presence of the bulky N-heterocyclic carbene derived from L-pyrogutamic acid, the reaction of ketenes with α-cyanochalcones went smoothly, giving the corresponding chiral multisubstituted dihydropyranones in good yields with good diastereoselectivities and high enantioselectivities. Initially, several NHCs derived from L-pyrogultamic acids were screened for the reaction. The NHC 4b with bulkyl dimethyl(tert-butyl)silyl group and N-isopropylphenyl performed better than others. The reaction catalyzed by NHCs 4c～4d with a free hydroxyl group gave the dihydropyranones with reversed diastereoselectivity but decreased enantioselectivity. The reaction went well in THF, toluene, dichloromethane or ether, while the one in toluene showed best results. Better yield was reached when the reaction was carried out at 0 or -20 ℃. Under optimized reaction conditions, a variety of aryl(alkyl)ketenes were investigated for the reaction. It was found that both electron-donating and electron-withdrawing groups in the aryl(alkyl)ketene are tolerable for the reaction. The one with electron-withdrawing substituent gave the product in better yield and diastereoselectivity, while the one with electron-donating substituent resulted in better enantioselectivity. The alkyl chain of the ketenes could be ethyl, n-propyl and n-butyl. All the α-cyanochalcones with para-, meta- or ortho-substitutent went well for the reaction. The absolute configuration of resulted dihydropyranone 3e was established by the X-ray analysis of its crystal. The reaction is proposed to initialize with the addition of NHC to ketenes to give the enolate I. The adduct Ⅱ is formed from enolate I and α-cyanochalcone via stepwise Michael addition and cyclization or simultaneous Diels-Alder reaction. The elimination of NHC from adduct Ⅱ gives final dihydropyranone 3.

Key words: N-heterocyclic carbenes, [4+2] cycloaddition, asymmetric catalysis, dihydropyranones

Cite this article

Sun Lihui, Liang Zhiqin, Ye Song. Asymmetric N-Heterocyclic Carbene-catalyzed [4+2] Cycloaddition of Ketenes with α-cyanochalcones[J]. Acta Chimica Sinica, 2014, 72(7): 841-844.

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References

[1] (a) Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606.
(b) Moore, J. L.; Rovis, T. Top. Curr. Chem. 2010, 291, 77.
(c) Bugaut, X.; Glorius, F. Chem. Soc. Rev. 2012, 41, 3511.
(d) Ryan, S. J.; Candish, L.; Lupton, D. W. Chem. Soc. Rev. 2013, 42, 4906.
(e) Mahatthananchai, J.; Bode, J. W. Acc. Chem. Res. 2014, 47, 696. For the examples of NHC as ligand for organometallic catalysts, see:
(f) Zhang, R.; Xu, Q.; Shi, M. Acta Chim. Sinica 2012, 70, 1593. (张睿, 徐琴, 施敏, 化学学报, 2012, 70, 1593.)
(g) Cheng, Y.; Sun, L. L. Chin. J. Org. Chem. 2012, 32, 511. (承勇, 孙礼林, 有机化学, 2012, 32, 511.)
(h) Gu, S. J.; Huang, J. J.; Chen, W. Z. Chin. J. Org. Chem. 2013, 33, 715. (顾绍金, 黄菁菁, 陈万芝, 有机化学, 2013, 33, 715.)
(i) Yang, L. R.; Wei, D.; Mai, W. P.; Mao, P. Chin. J. Org. Chem. 2013, 33, 943. (杨亮茹, 魏栋, 买文鹏, 毛璞, 有机化学, 2013, 33, 943.)

[2] (a) Sohn, S. S.; Rosen, E. L.; Bode, J. W. J. Am. Chem. Soc. 2004, 126, 14370.
(b) Bode, C.; Burstein.; Glorius, F. Angew. Chem. Int. Ed. 2004, 43, 6205.
(c) Nair, V.; Vellalath, S.; Poonoth M.; Mohan, R.; Suresh, E. Org. Lett. 2006, 8, 507.
(d) Hirano, K.; Piel, I.; Glorius, F. Adv. Synth. Catal. 2008, 350, 984.
(e) Li, Y.; Zhao, Z. A.; He, H.; You, S. L. Adv. Synth. Catal. 2008, 350, 1885.
(f) He, M.; Bode, J. W. Org. Lett. 2005, 7, 3131.
(g) Raup, D. E. A.; Cardinal-David, B.; Holte, D.; Scheidt, K. A. Nat. Chem. 2010, 2, 766.
(h) Zhao, X.; DiRocco, D. A.; Rovis, T. J. Am. Chem. Soc. 2011, 133, 12466.

[3] (a) Chan, A.; Scheidt, K. A. J. Am. Chem. Soc. 2007, 129, 5334.
(b) Phillips, E. M.; Reynolds, T. E.; Scheidt, K. A. J. Am. Chem. Soc. 2008, 130, 2416.

[4] (a) Nair, V.; Vellalath, S.; Poonoth, M.; Suresh, E. J. Am. Chem. Soc. 2006, 128, 8736.
(b) Chiang, P. C.; Kaeobamrung, J.; Bode, J. W. J. Am. Chem. Soc. 2007, 129, 3520.
(c) Kaeobamrung, J.; Bode, J. W. Org. Lett. 2009, 11, 677.
(d) Nair, V.; Paul, R. R.; Padmaja, D. V. M.; Aiswarya, N.; Sinu, C. R.; Jose, A. Tetrahedron 2011, 67, 9885. The α-lactam-fused cyclopentane was reported:
(e) He, M.; Bode, J. W. J. Am. Chem. Soc. 2008, 130, 418.

[5] (a) Kaeobamrung, J.; Kozlowski, M. C.; Bode, J. W. Proc. Natl. Acad. Sci. USA 2010, 107, 20661.
(b) Nair, V.; Paul, R. R.; Lakshmi, K. C. S.; Menon, R. S.; Jose, A.; Sinu, C. R. Tetrahedron Lett. 2011, 52, 5992;
(c) Fang, X.; Chen, X.; Chi, Y. R. Org. Lett. 2011, 13, 4708.
(d) He, M.; Struble, J. R.; Bode, J. W. J. Am. Chem. Soc. 2006, 128, 8418.
(e) Mo, J.; Chen, X.; Chi, Y. R. J. Am. Chem. Soc. 2012, 134, 8810.

[6] (a) He, M.; Uc, G. J.; Bode, J. W. J. Am. Chem. Soc. 2006, 128, 15088.
(b) He, M.; Beahm, B. J.; Bode, J. W. Org. Lett. 2008, 10, 3817

[7] (a) Kaeobamrung, J.; Mahatthananchai, J.; Zheng, P.; Bode, J. W. J. Am. Chem. Soc. 2010, 132, 8810.
(b) Zhu, Z. Q.; Xiao, J. C. Adv. Synth. Catal. 2010, 352, 2455.

[8] (a) Sun, F. G.; Sun, L. H.; Ye, S. Adv. Synth. Catal. 2011, 353, 3134;
(b) Yao, C. S.; Wang, D. L.; Lu, J.; Li, T. J.; Jiao, W. H.; Yu, C. X. Chem. Eur. J. 2012, 18, 1914.

[9] (a) Shen, L. T.; Shao, P. L.; Ye, S. Adv. Synth. Catal. 2011, 353, 193;
(b) Wang, T.; Ye, S. Scientia Sinica Chimica 2011, 41, 1306.
(b) Ryan, S. J.; Candish, L.; Lupton, D. W. J. Am. Chem. Soc. 2011, 133, 4694;
(c) Candish, L.; Lupton, D. W. J. Am. Chem. Soc. 2013, 135, 58.

[10] (a) Fu, Z.; Xu, J.; Zhu, T.; Leong, W. W. Y.; Chi, Y. R. Nat. Chem. 2013, 5, 835.
(b) Chi, R. Y. Org. Lett. 2013, 15,5823.
(c) Hao, L.; Du, Y.; Lv, H.; Chen, X.; Jiang, H.; Shao, Y.; Chi, Y. R. Org. Lett. 2012, 14, 2154.

[11] (a) Ryan, S. J.; Candish, L.; Lupton, D. W. J. Am. Chem. Soc. 2009, 131, 14176;
(b) Cheng, J.; Huang, Z.; Chi, Y. R. Angew. Chem. Int. Ed. 2013, 52, 8592.
(c) Xu, J.; Jin, Z.; Chi, Y. R. Org. Lett. 2013, 15, 5028.
(d) Chen, S.; Hao, L.; Zhang, Y.; Tiwari, B.; Chi, Y. R. Org. Lett. 2013, 15, 5822.

[12] (a) Awasthi, C.; Yadav, L. D. S. Synlett 2010, 1783.
(b) Atienza, R. L.; Roth, H. S.; Scheidt, K. A. Chem. Sci. 2011, 2, 1772.
(c) Kankala, S.; Vadde, R.; Vasam, C. S. Org. Biomol. Chem. 2011, 9, 7869.
(d) Sun, L. H.; Wang, T.; Ye. S. Chin. J. Chem. 2012, 30, 190.
(e) Cheng, X. Y.; Sun, L. H.; Ye, S. Chem. Eur. J. 2013, 19, 4441.

[13] (a) Zhang, Y. R.; He, L.; Wu, X.; Shao, P. L.; Ye, S. Org. Lett. 2008, 10, 277.
(b) Duguet, N.; Campbell, C. D.; Slawin, A. M. Z.; Smith,A. D. Org. Biomol. Chem. 2008, 6, 1108.

[14] (a) Zhang, Y. R.; Lv, H.; Zhou, D.; Ye, S. Chem. Eur. J. 2008, 14, 8473.
(b) Jian, T. Y.; Shao, P. L.; Ye, S. Chem. Commun. 2011, 47, 2381.
(c) Huang, X. L.; He, L.; Shao, P. L.; Ye, S. Angew. Chem. Int. Ed.2009, 48, 192.
(d) Shao, P. L.; Chen, X. Y.; Sun, L. H.; Ye, S. Tetrahedron Lett. 2010, 51, 2316.
(e) Lv, H.; Chen, X. Yu.; Sun, L. H.; Ye, S. J. Org. Chem. 2010, 75, 6973.
(f) Lv, H.; You, L.; Ye, S. Adv. Synth. Catal. 2009, 351, 2822.
(g) Jian, T. Y.; Chen, X. Y.; Sun, L. H.; Ye, S. Org. Biomol. Chem. 2013, 11, 158.

[15] (a) Juhl, K.; Jørgensen, K. A. Angew. Chem. 2003, 115, 1536.
(b) Boucard, V.; Broustal, G.; Campagne, J. M. Eur. J. Org. Chem. 2007, 225.
(c) Jørgensen, K. A. Angew. Chem. 2000, 112, 3702;Angew. Chem., Int. Ed. 2000, 39, 3558.
(d) Rong, Z. Q.; Jia, M. Q.; You, S. L. Tetrahedron. 2011, 67, 9329.
(e) Zhao, X. D.; Ruhl, K. E.; Rovis, T. Angew. Chem., Int. Ed. 2012, 51, 12330.
(f) Yang, L. M.; Wang, F.; Chua, P. J.; Lv, Y. B.; Zhong, L. J.; Zhong, G. F. Org. Lett. 2012, 14, 2894.
(g) Fu, Z. Q.; Sun, H.; Chen, S. J.; Tiwari, B.; Li, G. H.; Chi, Y. R. Chem. Commun. 2013, 49, 261.
(h) Allen, S. E.; Mahatthananchai, J.; Bode, J. W.; Kozlowski, M. C. J. Am. Chem. Soc. 2012, 134, 12098.
(i) Albrecht, L.; Dickmeiss, G.; Weise, C. F.; Jorgensen, K. A. Angew. Chem., Int. Ed. 2012, 51, 13109.
(j) Hao, X. Y.; Liu, X. H.; Li, W.; Tan, F.; Chu, Y. Y.; Zhao, X. H.; Lin, L. L.; Feng, X. M. Org. Lett. 2014, 16, 134.
(k) Mo, J.; Yang, R.; Chen, X.; Tiwari, B.; Chi, Y. R. Org. Lett. 2013, 15, 50.

氮杂环卡宾催化烯酮与氰基查尔酮的[4+2]不对称环加成反应