Enantioselective Aldol Reaction of Acetone and Benzofuran-2,3-diones†

doi:10.7503/cjcu20140052

Abstract

Abstract:

The 3-substituted 3-hydroxybenzofuran-2-one unit is encountered in a large variety of natural pro-ducts with a wide spectrum of biological activities. Therefore, development of new methodologies to the construction of chiral quaternary center at the 3-position of benzofuran-2-one compounds were highly desired. A highly enantioselective Aldol reaction of benzofuran-2,3-ones with ketone catalyzed by N-(2-thiophenesulfonyl)prolinamide through enamine activation strategy was developed. As a result, a number of chiral 3-hydro-xyl substituted benzofuran-2-ones derivatives were synthesized with very good yields(up to 96%) and mode-rate to good enantioselectivities(up to 91% e.e.). This methodology substantially broadens the benzofuranone chemistry and offer functionalized chiral products.

Key words: Benzofuran-2, 3-one, Chiral carbon center, Asymmetric catalysis, Aldol reaction

CLC Number:

O626.11

TrendMD:

LI Xin, HAN Yu, TAN Boxuan, WANG Bin, CHENG Jinpei. Enantioselective Aldol Reaction of Acetone and Benzofuran-2,3-diones^†[J]. Chem. J. Chinese Universities, 2014, 35(9): 1908.

Figures/Tables 6

References 31

[1]	Hussein. A. A., Meyer J. J. M., Jimeno M. L., Rodríguez B., J. Nat. Prod., 2007, 70, 293—295
[2]	Ge H. M., Zhu C. H., Shi D. H., Zhang L. D., Xie D. Q., Yang J., Ng S. W., Tan R. X., Chem. Eur. J., 2008, 14, 376—381
[3]	Nicolaou K. C., Wu T. R., Kang Q., Chen D. Y. K., Angew. Chem. Int. Ed., 2009, 48, 3440—3443
[4]	Nicolaou K. C., Kang Q., Wu T. R., Lim C. S., Chen D. Y. K., J. Am. Chem. Soc., 2010, 132, 7540—7548
[5]	Lü Z. L., Gao Y., Li J., Huang T. F., He S. J., Zou Y., Chem. J. Chinese Universities,2013, 34(11), 2531—2539
	(吕泽良, 高扬, 李军, 黄桐埅, 何树杰, 邹永. 高等学校化学学报, 2013, 34(11), 2531—2539)
[6]	CaY., Jiang X., Liu L., Shen F. , Zhang F. , Wang R., Angew. Chem. Int. Ed., 2011, 50, 9124—9127
[7]	Cheng X. F., Li Y., Su Y. M., Yin F., Wang J. Y., Sheng J., Vora H. U., Wang X. S., Yu J. Q., J. Am. Chem. Soc., 2013, 135, 1236—1239
[8]	Ohmatsu K., Ito M., Kunieda T., Ooi T., J. Am. Chem. Soc., 2013, 135, 590—593
[9]	Li X., Yang C., Jin J. L., Xue X. S., Cheng J. P., Chem. Asian J., 2013, 8, 997—1003
[10]	Li X., Zhang Y.Y., Xue X. S., Jin J. L., Tan B. X., Liu C., Dong N., Cheng J. P.,Eur. J. Org. Chem., 2012, 1774—1782
[11]	Li X., Xue X. S., Liu C., Wang B., Tan B. X., Jin J. L., Zhang Y. Y., Dong N., Cheng J. P., Org. Biomol. Chem., 2012, 10, 413—420
[12]	Liu C., Tan B. X., Jin J. L., Zhang Y. Y., Dong N., Li X., Cheng J. P., J. Org. Chem., 2011, 76, 5838—5845
[13]	Garduno-Ramırez M. L., Trejo A., Navarro V., Bye R., Linares E., Delgado G., J. Nat. Prod., 2001, 64, 432—435
[14]	Inman W. D., Luo J., Jolad S. D., King S. R., Cooper R., J. Nat. Prod., 1999, 62, 1088—1092
[15]	List B., Lerner R. A., Barbas C. F., J. Am. Chem. Soc., 2000, 122, 2395—2396
[16]	List B., Pojarliev P., Castello C., Org. Lett., 2001, 3, 573—575
[17]	Gröger H.,Wilken J., Angew. Chem. Int. Ed., 2001, 40, 529—532
[18]	List B., Tetrahedron, 2002, 58, 5573—5590
[19]	Pellissier H., Tetrahedron, 2007, 63, 9267—9331
[20]	Luppi G., Cozzi P. G., Monari M., Kaptein B., Broxterman Q. B., Tomasini C., J. Org. Chem., 2005, 70, 7418—7421
[21]	Guo Q. S., Bhanushali M., Zhao C. G., Angew. Chem. Int. Ed., 2010, 49, 9460—9464
[22]	Nakamura S., Hara N., Nakashima H., Kubo K., Shibata N., Toru T., Chem. Eur. J., 2008, 14, 8079—8081
[23]	Corrêa R.J., Garden S. J., Angelici G., Tomasini C.,Eur. J. Org. Chem., 2008, 736—744
[24]	Chen G., Wang Y., He H. P., Gao S., Yang X. S., Hao X. J., Heterocycles,2006, 68, 2327—2333
[25]	Malkov A. V., Kabeshov M. A., Bella M., Kysilka O., Malyshev D. A., Pluhackova K., Kocovsky P., Org. Lett., 2007, 9, 5473—5476
[26]	Pearson A. J., Panda S., Org. Lett., 2011, 13, 5548—5551
[27]	Luppi G., Monari M., Corrêa R. J., Violante F. A., Pinto A. C., Kaptein B., Broxterman Q. B., Gardenb S. J., Tomasini C., Tetrahedron,2006, 62, 12017—12024
[28]	Kale S. S., Kotmale A. S., Dutta A. K., Pal S., Rajamohanan P. R., Sanjayan G. J., Org. Biomol. Chem., 2012, 10, 8426—8433
[29]	Moorthy J.N., Saha S.,Eur. J. Org. Chem., 2009, 739—748
[30]	Wu Y. Y., Zhang Y. Z., Yu M. L., Zhao G., Wang S. W., Org. Lett., 2006, 8, 4417—4420
[31]	ZwanenburgD. J., Reynen W. A. P.,Synthesis, 1976, 624—625

Entry	Solvent	Time/d	Yield^b(%)	e.e.^c(%)	Entry	Solvent	Time/d	Yield^b(%)	e.e.^c(%)
1	THF	3	33	76	6	1,4-Dioxane	3	76	76
2	DCM	3	71	34	7	Toluene	3	59	56
3	Acetone	3	71	43	8	n-Hexane	3	40	62
4	Acetonitrile	3	48	34	9	DMF	3	86	86
5	Ethanol	3	73	46	10	DMSO	3	85	91

Entry	Solvent	Time/d	Yield^b(%)	e.e.^c(%)	Entry	Solvent	Time/d	Yield^b(%)	e.e.^c(%)
1	THF	3	33	76	6	1,4-Dioxane	3	76	76
2	DCM	3	71	34	7	Toluene	3	59	56
3	Acetone	3	71	43	8	n-Hexane	3	40	62
4	Acetonitrile	3	48	34	9	DMF	3	86	86
5	Ethanol	3	73	46	10	DMSO	3	85	91

Entry	Substrate	Time/d	Compd.	Yield^b(%)	e.e.^c(%)	Entry	Substrate	Time/d	Compd.	Yield^b(%)	e.e.^c(%)
1	1a	3	3a	85	91	5	1e	11	3e	80	84
2	1b	11	3b	73	75	6	1f	14	3f	74	30
3	1c	11	3c	96	86	7	1g	14	3g	60	14
4	1d	11	3d	65	76

Entry	Substrate	Time/d	Compd.	Yield^b(%)	e.e.^c(%)	Entry	Substrate	Time/d	Compd.	Yield^b(%)	e.e.^c(%)
1	1a	3	3a	85	91	5	1e	11	3e	80	84
2	1b	11	3b	73	75	6	1f	14	3f	74	30
3	1c	11	3c	96	86	7	1g	14	3g	60	14
4	1d	11	3d	65	76