Copper Catalyzed[3+2] Annulation of Indoles with 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes

doi:10.6023/A17040146

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (8): 783-787.DOI: 10.6023/A17040146 Previous Articles Next Articles

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铜(II)催化的吲哚与四取代D-A环丙烷[3+2]开环/环化反应

严文广, 王盼, 王丽佳, 孙秀丽, 唐勇

中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2017-04-07 发布日期:2017-06-15
通讯作者: 孙秀丽,E-mail:xlsun@sioc.ac.cn;唐勇,tangy@sioc.ac.cn E-mail:xlsun@sioc.ac.cn;tangy@sioc.ac.cn
基金资助:
项目受国家自然科学基金（Nos.21432011，21421091）、国家重点基础研究发展计划项目（973项目，No.2015CB856600）、中国科学院战略性先导科技专项（B类）资助（No.XDB20000000）、中国科学院青年促进会（No.2017301）以及上海市自然科学基金（No.17ZR1436900）资助.

Copper Catalyzed[3+2] Annulation of Indoles with 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes

Yan Wen-Guang, Wang Pan, Wang Lijia, Sun Xiu-Li, Tang Yong

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2017-04-07 Published:2017-06-15
Contact: 10.6023/A17040146 E-mail:xlsun@sioc.ac.cn;tangy@sioc.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos.21421091 and 21432011),the National Basic Research Program of China (973 Program)(No.2015CB856600),the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No.XDB20000000),the Youth Innovation Promotion Association CAS (No.2017301) and the Natural Science Foundation of Shanghai (No.17ZR1436900).

1. Copper Catalyzed[3+2] Annulation of Indoles with 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes.PDF(4192KB)

Abstract

D-A cyclopropanes have emerged as versatile synthons for construction of carbocycles and heterocycles via a[3 +2] annulation reactions, and have been used in the total synthesis of natural products. Recently, it has been witnessed tremendous progress within the area of transformation of 2-monosubstituted-cyclopropane-1,1-diesters. However, cyclopropane-1,1-diesters with full substitution at the donor site have not been well explored. C2, C3-fused indolines are widely existed in a plenty of natural products and biologically active compounds, and have been the synthetic targets for decades. Among the various approaches to access these important structural motifs, the cyclopentannulation of indoles with Donor-Acceptor (D-A) cyclopropanes, represents a concise, economical and effective method. Previously, we have developed a highly diastereo-and enantioselective BOX/Cu(Ⅱ) catalyzed C2, C3-cyclopentannulation of indoles with 2-monosubstituted-cyclopropane-1,1-diesters, a facile access to a series of enantioenriched cyclopenta-fused indoline products. As our further studies, Lewis acid catalyzed[3+2] annulation of indoles with 1,1,2,2-tetrasubstituted D-A cyclopropanes was reported in this paper. This annulation method of C3-substituted indoles with quaternary donor site D-A cyclopropanes yielded C2, C3-fused indolines, bearing three quaternary stereocentres on the newly built cyclopentane ring without the formation of the common Friedel-Crafts byproducts. The ester groups on cyclopropane, ligand, and protection group of indole have great influence on both yield and dr selectivity. Thus, the reaction between indole (1b, -NMe) and cyclopropane 2 (CO₂R²=CO₂CH₂CF₃) can give the highest yield and the best dr in the presence of 10 mol% BOX/Cu(SbF₆)₂ in DCM, which is prepared in situ. Under the optimal conditions, the[3+2] annulation reacts smoothly with a wide range of substituted indole derivatives and D-A cyclopropanes, giving the desired products in up to 91% yield with up to >20/1 diastereoselectivity. The relative configuration of the products is determined by X-ray crystallographic analysis of the major diastereoisomer of 3b. The general experimental procedure for the[3+2] annulations is shown below:A mixture of CuBr₂(0.02 mmol), AgSbF₆ (0.04 mmol), and bisoxazoline (L,0.024 mmol) in DCM (1 mL) was stirred at room temperature for 3 h under the atmosphere of nitrogen. Then, the mixture was cooled to 0℃ for 20 min and the cyclopropane 1(0.2 mmol) and the indole derivative 2 (0.4 mmol) in 1 mL DCM were added to the mixture of catalyst via a syringe. After the reaction was complete (monitored by TLC), the reaction was filtered through a glass funnel with thin layer (20 mm) of silica gel (100~200 mesh) and eluted with DCM (approx 100 mL). The filtrate was concentrated under reduced pressure. After the determination of the diatereoselectivity by ¹H NMR, the residue was purified by flash chromatography to afford the product 3.

Key words: Donor-Acceptor (D-A) cyclopropane, indole, annulation, quaternary center, bis-oxazoline

Cite this article

Yan Wen-Guang, Wang Pan, Wang Lijia, Sun Xiu-Li, Tang Yong. Copper Catalyzed[3+2] Annulation of Indoles with 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes[J]. Acta Chim. Sinica, 2017, 75(8): 783-787.

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References

[1] For reviews on the transformations of D-A cyclopropanes, see:(a)Reissig, H.-U.; Zimmer, R. Chem. Rev. 2003, 103, 1151;
(b) Yu, M.; Pagenkopf, B. L. Tetrahedron 2005, 61, 321;
(c) Rubin, M.; Rubina, M.; Gevorgyan, V. Chem. Rev. 2007, 107, 3117;
(d) Carson, C. A.; Kerr, M. A. Chem. Soc. Rev. 2009, 38, 3051;
(e) Cavitt, M. A.; Phun, L. H.; France, S. Chem. Soc. Rev. 2014, 43, 804;
(f) de Nanteuil, F.; De Simone, F.; Frei, R.; Benfatti, F.; Serrano, E.; Waser, J. Chem. Commun. 2014, 50, 10912;
(g) Liao, S.; Sun, X.-L.; Tang, Y. Acc. Chem. Res. 2014, 47, 2260;
(h) Schneider, T. F.; Kaschel, J.; Werz, D. B. Angew. Chem., Int. Ed. 2014, 53, 5504;
(i) Grover, H. K.; Emmett, M. R.; Kerr, M. A. Org. Biomol. Chem. 2015, 13, 655.
(j) Wang, Y.; Yu, Z.-X. Acc. Chem. Res. 2015, 48, 2288.
[2] For selected examples, see:(a) Meyers, C.; Carreira, E. M. Angew. Chem., Int. Ed. 2003, 42, 694;
(b) Carson, C. A.; Kerr, M. A. Angew. Chem., Int. Ed. 2006, 45, 6560;
(c) Young, I. S.; Kerr, M. A. J. Am. Soc. Chem. 2007, 129, 1465;
(d) Leduc, A. B.; Kerr, M. A. Angew. Chem., Int. Ed. 2008, 47, 7945;
(e) Morales, C. L.; Pagenkopf, B. L. Org. Lett. 2008, 10, 157.
(f) Campbell, M. J.; Johnson, J. S. J. Am. Soc. Chem. 2009, 131, 10370;
(g) Karadeolian, A.; Kerr, M. A. Angew. Chem., Int. Ed. 2010, 49, 1133;
(h) Han, Y.; Fu, Q.; Tang, W.; Yan, C. Chin. J. Chem. 2012, 30, 1867.
[3] For recent selected examples, see:(a) Grover, H. K.; Emmett, M. R.; Kerr, M. A. Org. Lett. 2013, 15, 4838;
(b) Haubenreisser, S.; Hensenne, P.; Schröder, S.; Niggemann, M. Org. Lett. 2013, 15, 2262;
(c) Miyake, Y.; Endo, S.; Moriyama, T.; Sakata, K.; Nishibayashi, Y. Angew. Chem., Int. Ed. 2013, 52, 1758;
(d) Ryabchuk, P.; Edwards, A.; Gerasimchuk, N.; Rubina, M.; Rubin, M. Org. Lett. 2013, 15, 6010;
(e) Wales, S. M.; Walker, M. M.; Johnson, J. S. Org. Lett. 2013, 15, 2558;
(f) Xiong, H.; Xu, H.; Liao, S.; Xie, Z.; Tang, Y. J. Am. Soc. Chem. 2013, 135, 7851;
(g) Zhou, Y.-Y.; Li, J.; Ling, L.; Liao, S.-H.; Sun, X.-L.; Li, Y.-X.; Wang, L.-J.; Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 1452;
(h) Chakrabarty, S.; Chatterjee, I.; Wibbeling, B.; Daniliuc, C. G.; Studer, A. Angew. Chem., Int. Ed. 2014, 53, 5964;
(i) de Nanteuil, F.; Serrano, E.; Perrotta, D.; Waser, J. J. Am. Soc. Chem. 2014, 136, 6239;
(j) Garve, L. K. B.; Barkawitz, P.; Jones, P. G.; Werz, D. B. Org. Lett. 2014, 16, 5804;
(k) Hashimoto, T.; Kawamata, Y.; Maruoka, K. Nat. Chem. 2014, 6, 702;
(l) Lin, S.; Li, L.; Liang, F.; Liu, Q. Chem. Commun. 2014, 50, 10491;
(m) Novikov, R. A.; Tarasova, A. V.; Korolev, V. A.; Timofeev, V. P.; Tomilov, Y. V. Angew. Chem., Int. Ed. 2014, 53, 3187;
(n) Talukdar, R.; Tiwari, D. P.; Saha, A.; Ghorai, M. K. Org. Lett. 2014, 16, 3954;
(o) Zhang, H.-H.; Luo, Y.-C.; Wang, H.-P.; Chen, W.; Xu, P.-F. Org. Lett. 2014, 16, 4896;
(p) Kang, Q.-K.; Wang, L.; Zheng, Z.-B; Li, J.-F.; Tang, Y. Chin. J. Chem. 2014, 32, 669;
(q) Liu, H.; Zheng, C.; You, S.-L. Chin. J. Chem. 2014, 32, 709;
(r) Chen, H.; Zhang, J.; Wang, D. Z. Org. Lett. 2015, 17, 2098;
(s) Rakhmankulov, E. R.; Ivanov, K. L.; Budynina, E. M.; Ivanova, O. A.; Chagarovskiy, A. O.; Skvortsov, D. A.; Latyshev, G. V.; Trushkov, I. V.; Melnikov, M. Y. Org. Lett. 2015, 17, 770;
(t) Xia, Y.; Liu, X.; Zheng, H.; Lin, L.; Feng, X. Angew. Chem., Int. Ed. 2015, 54, 227;
(u) Xu, H.; Hu, J.-L.; Wang, L.; Liao, S.; Tang, Y. J. Am. Soc. Chem. 2015, 137, 8006;
(v) Wang, L.-N.; Cui, Q.; Yu, Z.-X. J. Org. Chem. 2016, 81, 10165;
(w) Bose, S.; Yang, J.; Yu, Z.-X. J. Org. Chem. 2016, 81, 6757;
(x) Liu, C.-H.; Yu, Z.-X. Org. Biomol. Chem. 2016, 14, 5945;
(y) Liu, C.-H.; Zhuang, Z.; Bose, S.; Yu, Z.-X. Tetrahedron 2016, 72, 2752.
[4] For examples on transformations of 1,1,2,2-tetrasubstituted Donor-Acceptor Cyclopropanes, see:(a) Sibi, M. P.; Ma, Z.; Jasperse, C. P. J. Am. Chem. Soc. 2005, 127, 5764;
(b) Carson, C. A.; Kerr, M. A. Org. Lett. 2009, 11, 777;
(c) Sherry, B. D.; Furstner, A. Chem. Commun. 2009, 7116;
(d) Xing, S.; Pan, W.; Liu, C.; Ren, J.; Wang, Z. Angew. Chem., Int. Ed. 2010, 49, 3215;
(e) Smith, A. G.; Slade, M. C.; Johnson, J. S. Org. Lett. 2011, 13, 1996;
(f) Yu, Q.; Ma, S. Chem. Commun. 2012, 48, 11784;
(g) Wenz, D. R.; Read de Alaniz, J. Org. Lett. 2013, 15, 3250;
(h) Zhu, W.; Fang, J.; Liu, Y.; Ren, J.; Wang, Z. Angew. Chem., Int. Ed. 2013, 52, 2032;
(i) Mackay, W. D.; Fistikci, M.; Carris, R. M.; Johnson, J. S. Org. Lett. 2014, 16, 1626;
(j) Shiba, T.; Kuroda, D.; Kurahashi, T.; Matsubara, S. Synlett 2014, 25, 2005.
[5] (a) Dewick, P. M. Medicinal Natural Products:A Biosynthetic Approach, 2nd ed., Wiley, New York, 2002;
(b) Fattorusso, E.; Taglialatela Scafati, O. Modern Alkaloids, Wiley-VCH, Weinheim, Germany, 2008.
[6] For selected annulations of indoles with cyclopropanes, see:(a) Harrington, P.; Kerr, M. A. Tetrahedron Lett. 1997, 38, 5949;
(b) Kerr, M. A.; Keddy, R. G. Tetrahedron Lett. 1999, 40, 5671;
(c) England, D. B.; Kuss, T. D. O.; Keddy, R. G.; Kerr, M. A. J. Org. Chem. 2001, 66, 4704;
(d) Bajtos, B.; Yu, M.; Zhao, H.; Pagenkopf, B. L. J. Am. Soc. Chem. 2007, 129, 9631.
[7] For selected examples of using L as ligand:(a) Yasuhara, S.; Sasa, M.; Kusakabe, T.; Takayama, H.; Kimura, M.; Mochida, T.; Kato, K. Angew. Chem., Int. Ed. 2011, 50, 3912;
(b) Zhou, J.-L.; Liang, Y.; Deng, C.; Zhou, H.; Wang, Z.; Sun, X.-L.; Zheng, J.-C.; Yu, Z.-X.; Tang, Y. Angew. Chem., Int. Ed. 2011, 50, 7874;
(c) Karyakarte, S. D.; Smith, T. P.; Chemler, S. R. J. Org. Chem. 2012, 77, 7755;
(d) Miller, Y.; Miao, L.; Hosseini, A. S.; Chemler, S. R. J. Am. Chem. Soc. 2012, 134, 12149;
(e) Qu, J.-P.; Liang, Y.; Xu, H.; Sun, X.-L.; Yu, Z.-X.; Tang, Y. Chem.-Eur. J. 2012, 18, 2196;
(f) Del Bel, M.; Rovira, A.; Guerrero, C. A. J. Am. Chem. Soc. 2013, 135, 12188.

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铜(II)催化的吲哚与四取代D-A环丙烷[3+2]开环/环化反应

Copper Catalyzed[3+2] Annulation of Indoles with 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes

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