Synthesis of Functionalized Enamines(Ⅳ): β,β-Dicyanostyrene Derivatives Reacted with NBS Converted into Corresponding Enamines Promoted by NaOAc†

doi:10.7503/cjcu20140218

Abstract

Abstract:

An easy and efficient new method for the expeditious synthesis of functionalized enamines from β,β-dicyanostyrene derivatives reacted with N-bromosuccinimide(NBS) was developed. The β,β-dicyanostyrene derivatives were smoothly converted into corresponding functionalized enamines promoted by NaOAc(200%, molar fraction) in DMF at room temperature in good to excellent yield within 80 min. This new method has many advantages such as mild conditions, easy handling, nearly quantitative yields 12 substrates with different structures were investigated. The results indicated that the protocol has applicability in a large scope of the electron-deficient olefins. A possible addition-elimination pathway was proposed and it explained well the full regiospecificity of the reaction. The structures of all products were confirmed by their ¹H NMR, ¹³C NMR and HRMS analysis.

Key words: β,β-Dicyanostyrene derivative, Functionalized enamine, NaOAc

CLC Number:

O626.3

TrendMD:

CHEN Zhanguo, LIU De’e, LI Wenli, LIU Yali. Synthesis of Functionalized Enamines(Ⅳ): β,β-Dicyanostyrene Derivatives Reacted with NBS Converted into Corresponding Enamines Promoted by NaOAc^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2360.

Figures/Tables 6

References 31

[1]	Chen Z. G., Wang Y., Wei J. F., Zhao P. F., Shi X. Y., J. Org. Chem., 2010, 75(6), 2085—2088
[2]	Chen Z. G., Zhou L. Y., Li W. L., Zhou J. M., Wang C. N., Acta Chim. Sinica,2011, 69(9), 1093—1100
	(陈战国, 周利燕, 李文丽, 周继梅, 王传宁. 化学学报,2011, 69(9), 1093—1100)
[3]	Chen Z. G., Zhou J. M., Wang Y., Li W. L., Acta Chim. Sinica,2011, 69(23), 2851—2858
	(陈战国, 周继梅, 王芸, 李文丽. 化学学报,2011, 69(23), 2851—2858)
[4]	Chen Z. G., Hu J. L., Xia W., Wang D., Li Y. N., Chem. J. Chinese Universities,2013, 34(5), 1151—1159
	(陈战国, 胡均利, 夏伟, 王丹, 李亚男. 高等学校化学学报,2013, 34(5), 1151—1159)
[5]	Chen Z. G., Xia W., Wen H., Wang D., Li Y. N., Hu J. L., Chem. Res. Chinese Universities,2013, 29(4), 699—705
[6]	Li W. L., Chen Z. G., Zhou J. M., Hu J. L., Xia W., Chin. J. Chem., 2012, 30(4), 830—836
[7]	Chen Z. G., Li Y. N., Zhou J. M., Wang D., Ge M., Chem. Res. Chinese Universities,2014, 30(2), 266—271
[8]	Ferreira P. M. T., Monteiro L. S., Coban T., Suzen S., Journal of Enzyme Inhibition and Medicinal Chemistry,2009, 24(4), 967—971
[9]	Kong Y., Yang W., Wu W. T., Pharm. Biotechnol., 2007, 14(3), 230—234
	(孔毅, 杨婉, 吴梧桐. 药物生物技术, 2007, 14(3), 230—234)
[10]	Zhou H., Donk W. A., Org. Lett., 2001, 3(4), 593—596
[11]	Zhou H., Donk W. A., Org. Lett., 2002, 4(8), 1335—1338
[12]	Sibi M. P., Asano Y., Sausker J. B., Angew. Chem. Int. Ed., 2001, 40(7), 1293—1296
[13]	Miossec B., DanionBougot R., Danion D.,Synthesis, 1994, (11), 1171—1174
[14]	Burk M. J., Allen J. G., Kiesman W. F. Stoffan K. M., Tetrahedron Lett., 1997, 38(8), 1309—1312
[15]	Manzoni L., Colombo M., Scolastico C., Tetrahedron Lett., 2004, 45(12), 2623—2625
[16]	Horikawa H., Nishitani T., Iwasaki T., Mushika Y., Inoue I., Miyoshi M., Tetrahedron Lett., 1980, 21(42), 4101—4104
[17]	Bartels A., Peter G. J., Liebscher J., Tetrahedron Lett., 1995, 36(21), 3673—3674
[18]	Bartels A., Jones P. G., Liebscher J.,Synthesis, 2003, (1), 67—72
[19]	Tang W., Zhang X., Chem. Rev., 2003, 103(8), 3029—3070
[20]	Chen W. P., Mbafor W., J. Am. Chem. Soc., 2006, 128(12), 3922—3923
[21]	Ferreira P. M. T., Maia H. L. S., Monteiro L. S., Tetrahedron Lett., 1999, 40(21), 4099—4102
[22]	Abreu A. S., Silva N. O., Ferreira P. M. T., Queiroz M. R. P., Eur. J. Org. Chem., 2003, (8), 1537—1544
[23]	Tu S. J., Rong L. C., Gao Y., Guo S. M., Lu S. H., Yang X. J., Chin. J. Org. Chem., 2002, 22(5), 364—366
	(屠树江, 荣良策, 高原, 郭苏闵, 鲁水华, 杨晓洁. 有机化学, 2002, 22(5), 364—366)
[24]	Kalbasi R. J., Kolahdoozan M., Vanani S. M., J. Solid State Chem., 2011, 184(8), 2009—2016
[25]	Li G. W., Xiao J., Zhang W. Q., Green Chem., 2011, 13(7), 1828—1836
[26]	Mona H. S., Hashem S., Samane E., Chin. J. Chem., 2007, 25(10), 1563—1567
[27]	Yue C. B., Mao A. Q., Wei Y. Y., Lue M. J., Catal. Commun., 2008, 9(7), 1571—1574
[28]	Wiles C., Watts P., Haswell S. J., Tetrahedron,2004, 60(38), 8421—8427
[29]	Kharas G. B., Hanawa E., Hill B. L., Flynn K. T., Furlan L. N., Holtrup B., Jackson A. T., Kalayil A. T., Kelliher M. T., Kostaken J. J., Atlasb S., Raihaneb M., J. Macromol. Sci., Part A: Pure & Applied Chem., 2011, 48(2), 91—94
[30]	Karmakar B., Chowdhury B., Banerji J., Catal. Commun., 2010, 11(7), 601—605
[31]	Lin Q., Chen P., Fu Y. P., Zhang Y. M., Shi B. B., Zhang P., Wei T. B., Chinese Chem. Lett., 2013, 24(8), 699—702

Compd.	m.p./℃	Compd.	m.p./℃
1a	167—168 (167—168^[24])	1g	115—116.8 (110—112^[25])
1b	128.3 (125—127^[25])	1h	93—94 (102—104^[25])
1c	164.3—164.7 (166—168^[26])	1i	93.4—94.2 (85^[28], 100^[29] )
1d	152—153 (153—154^[24])	1j	143.2—114.5 (140^[30])
1e	132.8—133.8 (132—134^[24])	1k	167.2—167.7 (168—169^[31])
1f	82.5—83.6 (82—84^[27])	1l	69.8—71 (70—72^[25])

Compd.	m.p./℃	Compd.	m.p./℃
1a	167—168 (167—168^[24])	1g	115—116.8 (110—112^[25])
1b	128.3 (125—127^[25])	1h	93—94 (102—104^[25])
1c	164.3—164.7 (166—168^[26])	1i	93.4—94.2 (85^[28], 100^[29] )
1d	152—153 (153—154^[24])	1j	143.2—114.5 (140^[30])
1e	132.8—133.8 (132—134^[24])	1k	167.2—167.7 (168—169^[31])
1f	82.5—83.6 (82—84^[27])	1l	69.8—71 (70—72^[25])