Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine†

doi:10.7503/cjcu20140136

Abstract

Abstract:

Asymmetric conjugate addition of 1-bromonitromethane tobenzylidene acetone was catalyzed by 9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst. We had identified a detailed mechanism of the title reaction with density functional theory(B3LYP and M062X) and ab initio calculations(MP2). The reaction process includes three major stages: (1) the formation of an iminium ion intermediate; (2) the nucleophilic addition between the iminium and 1-bromonitromethane; (3) hydrolysis and recovery of catalyst. The calculated results not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general model to help explain the mechanism and enantioselectivity of the conjugate addition reaction.

Key words: Density functional theory, Ab initio calculation, Mechanism of asymmetric conjugate addition, Enantioselectivity, 9-Amino-9-deoxyepiquinine

CLC Number:

O641

TrendMD:

JIANG Haiyang, FENG Wei, SUN Yanwei, QI Qiaofang, TIAN Hongwei, LIU Huiling, HUANG Xuri. Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1500.

Figures/Tables 10

Fig.1 Mechanism A for the formation of the iminium intermediates[27]

Fig.2 Mechanism B for the formation of the iminium intermediates

Fig.3 Optimized geometries and selected geometric parameters for the formation of iminium intermediate Some hydrogen atoms of the catalyst not involved in reaction sites are omitted; distances are in nm.

Fig.4 Bond dissociation curves calculated via point-wise optimized method at the B3LYP/6-31+G(d,p) level of theory

Fig.5 Relative energy profile for the formation of iminium intermediate Values of ΔG are given in parentheses.

Fig.6 Optimized geometries and selected geometric parameters for the addition reaction etween iminium intermediate and 1-bromonitromethane

Fig.7 Optimized geometries and selected geometric parameters for the hydrolysis and regeneration of the catalyst Some hydrogen atoms not involved in reaction sites are omitted; distances are in nm.

Fig.8 Four pathways to the S or R enantiomers, respectively

Fig.9 Relative energy profiles for the addition reaction for the real reaction system Values of ΔE are given in parentheses and ΔG in brackets.

Fig.10 Relative energy profiles for the hydrolysis to obtain the final product for the real reaction system Values of ΔE are given in parentheses and ΔG in brackets.

References 28

[1]	Dalko P. I., Moisan L., Angew. Chem. Int. Ed., 2004, 43(39), 5138—5175
[2]	Seayad J., List B., Org. Biomol. Chem., 2005, 3(5), 719—724
[3]	Zhang Q. Y., Zhang D. D., Suo J. J., Li J. Y., Long H. L., Xu L., Chem. J. Chinese Universtities, 2012, 33(7), 1413—1419
	(张庆友, 张丹丹, 索净洁, 李静亚, 龙海林, 许禄.高等学校化学学报, 2012, 33(7), 1413—1419)
[4]	Pei W., Chem. J. Chinese Universtities, 1998, 19(3), 402—405
	(裴文. 高等学校化学学报, 1998, 19(3), 402—405)
[5]	List B.,Chem. Commun., 2006, (8), 819—824
[6]	Xu L.W., Luo J., Lu Y. X.,Chem. Commun., 2009, (14), 1807—1821
[7]	Xie J. W., Chen W., Li R., Zeng M., Du W., Yue L., Chen Y. C., Wu Y., Deng J. G., Angew. Chem., 2007, 119(3), 393—396
[8]	Martin N. J. A., List B., J. Am. Chem. Soc., 2006, 128(41), 13368—13369
[9]	Dong L. T., Lu R. J., Du Q. S., Zhang J. M., Xuan Y. N., Yan M., Tetrahedron, 2009, 65(21), 4124—4129
[10]	Gonzalez C., Schlegel H. B., J. Chem. Phys., 1989, 90(4), 2154—2161
[11]	Gonzalez C., Schlegel H. B., J. Phys. Chem., 1990, 94(14), 5523—5527
[12]	Reed A. E., Curtiss L. A., Weinhold F., Chem. Rev., 1988, 88(6), 899—926
[13]	Reed A. E., Weinstock R. B., Weinhold F., J. Chem. Phys., 1985, 83(2), 735—746
[14]	Jones G. O., Li X., Hayden A. E., Houk K. N., Danishefsky S. J., Org. Lett., 2008, 10(18), 4093—4096
[15]	Peles D. N., Thoburn J. D., J. Org. Chem., 2008, 73(8), 3135—3144
[16]	Rehbein J., Hiersemann M., J. Org. Chem., 2009, 74(11), 4336—4342
[17]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Kitao O., Li X., Knox J. E., Hratchian H. P., Cross J. B., Adamo C., Jaramillo J., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., AlLaham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 03, Revision B. 05, Gaussian Inc., Pittsburgh PA, 2003
[18]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Challacombe M., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 09, Revision A. 1, Gaussian Inc.Wallingford CT, 2009
[19]	Oliva C.G., Silva A. M. S., Resende D. I. S. P., Paz F. A. A., Cavaleiro J. A. S.,Eur. J. Org. Chem., 2010, (18), 3449—3458
[20]	Yao C. F., Sun C. X., Yan S. Y., Wu H. H., Prog. Chem., 2008, 20(6), 887—898
	(姚成福, 孙彩霞, 闫少宇, 吴海虹. 化学进展, 2008, 20(6), 887—898 )
[21]	Yang K., Xu M., Huang Z. P., Gan G. L., Chemical Industry of Guangzhou, 2009, 37(3), 51—54
	(杨昆, 徐梦, 黄志平, 甘桂莲. 广州化工, 2009, 37(3), 51—54 )
[22]	Huang H., Jacobsen E. N., J. Am. Chem. Soc., 2006, 128(22), 7170—7171
[23]	Wei S., Yalavov D. A., Tsogoeva S. B., Schmatz S., Catal. Today, 2007, 121(2), 151—157
[24]	Peng F., Shao Z., J. Mol. Catal. A, 2008, 285(1), 1—14
[25]	Xu L.W., Luo J., Lu Y. X.,Chem. Commun., 2009, (14), 1807—1821
[26]	Jiang L., Chen Y. C., Catal. Sci. Technol., 2011, 1(3), 354—365
[27]	Su Z., Lee H. W., Kim C. K., Eur. J. Org. Chem., 2013, 2013(9), 1706—1715
[28]	Wang X. P., Wang X. Z., Wang X. K., Liu Z. Q., Niu J. H., Univ. Chem., 2011, 26(3),33—37(王新平, 王旭珍, 王新葵, 刘泽群, 牛家豪. 大学化学, 2011, 2011, 26(3), 33—37)