不对称双酸催化吲哚的Friedel-Crafts烷基化反应：抗衡阴离子调控对映选择性

doi:10.6023/A14040246

摘要/Abstract

研究了双酸催化剂对吲哚和β，γ-不饱和α-酮酸酯的不对称Friedel-Crafts烷基化反应. 金属铟（Ⅲ）盐和手性磷酸组成的双酸催化体系可以高效、高选择性地催化吲哚与β，γ-不饱和α-酮酸酯的Friedel-Crafts烷基化反应. 简单改变铟（Ⅲ）盐的抗衡阴离子从F^-到Br^-，就能使产物的构型发生反转，并同时获得相应的高产率（最高达98%）和高对映选择性（最高大于99%）的1，4-加成产物.

关键词: 不对称催化, Friedel-Crafts烷基化反应, 手性反转, 双酸, 抗衡阴离子效应

Effective access to both enantiomers of any targeted products from a single chiral source of catalyst is highly desirable in asymmetric catalysis. Such dual stereocontrol has normally been encountered with structural modifications on the chiral ligands or catalysts skeletons. Recently, simple variations of reactions conditions such as solvents, temperature, additive and catalytic metal center, can lead to remarkable reversal of enantioselectivity with minimum structural modifications, thus providing a modular and synthetic appealing approach in asymmetric catalysis and synthesis. Previously, we have developed asymmetric binary acid catalysis wherein chiral Brønsted acids, mostly phosphoric acids, are utilized as dual acids and ligands in concert with metal catalysts, and this type of catalysis demonstrated tunable, even switchable stereoselectivity due to the combinatorial and synergistic features. In particular, simple swap of counteranion (from F^- to Br^-) of Indium(Ⅲ) salts led to complete switch of regioselectivity (1,2- vs. 1,4- addition) in the reaction of N-methyl indole 2a' and ketoester 3a with high enantioselectivity achieved for both regioisomers. In our further studies, we have found that when indole 2a was employed instead of N-methyl indole 2a', the counter anion effect on regioselectivity was not observed and both InF₃ and InBr₃ promoted exclusively 1,4-addition reactions. Interestingly, reversal of enantioselectivity of the 1,4-conjugate adduct was observed by simple swap of counter anions of indium(Ⅲ). The obtained optimal binary-acids combination, InF₃(1c)₂ and InBr₃(1d)₂ were found to be R- and S-selective catalyst for the 1,4-addition reactions, respectively. In the presence of asymmetric binary-acid catalysts (InX₃/1, 2.5 mol%), indoles and β,γ-unsaturated α-ketoesters were stirred at -70 ℃ for 24 h to afford the various indole esters 4 in good to excellent yield (up to 98% yield ) and enantioselectivities (up to>99% ee).

Key words: asymmetric catalysis, Friedel-Crafts alkylation, switchable enantioselectivity, binary-acid, counter anion effect

引用此文

吕健, 秦岩, 程津培, 罗三中. 不对称双酸催化吲哚的Friedel-Crafts烷基化反应：抗衡阴离子调控对映选择性[J]. 化学学报, 2014, 72(7): 809-814.

LÜ Jian, Qin Yan, Cheng Jinpei, Luo Sanzhong. Counteranions of In(Ⅲ) Induced Reversal of Enantiocontrol in Friedel-Crafts Reaction of Indoles by Asymmetric Binary Acid Catalysis[J]. Acta Chimica Sinica, 2014, 72(7): 809-814.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] For recent reviews, see: (a) Noyori, R. Chem. Soc. Rev. 1989, 18, 187;

(b) Comprehensive Asymmetric Catalysis, Eds.: Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H., Springer, Berlin, 1999;

(c) Catalytic Asymmetric Synthesis, Ed.: Ojima, I., Wiley-VCH, New York, 2000.

(d) Zanoni, G.; Castronovo, F.; Franzini, M.; Vidari, G.; Giannini, E. Chem. Soc. Rev. 2003, 32, 115;

(e) Tanaka, T.; Hayashi, M. Synthesis 2008, 3361;

(f) Bartók, M. Chem. Rev. 2010, 110, 1663;

(g) Escorihuela, J.; Burguete, M. I.; Luis, S. V. Chem. Soc. Rev. 2013, 42, 5595.

[2] For selected examples for control with solvent: (a) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 4545;

(b) Arseniyadis, S.; Valleix, A.; Wagner, A.; Mioskowski, C. Angew. Chem., Int. Ed. 2004, 43, 3314;

(c) Arseniyadis, S.; Subhash, P. V.; Valleix, A.; Mathew, S. P.; Blackmond, D. G.; Wagner, A.; Mioskowski, C. J. Am. Chem. Soc. 2005, 127, 6138;

(d) Sohtome, Y.; Tanaka, S.; Takada, K.; Yamaguchi, T.; Nagasawa, K. Angew. Chem., Int. Ed. 2010, 49, 9254;

(e) Zhou, J.; Ye, M.-C.; Huang, Z.-Z.; Tang, Y. J. Org. Chem. 2004, 69, 1309.

[3] For selected examples for control with temperature: (a) Inoue, Y.; Yokoyama, T.; Yamasaki, N.; Tai, A. Nature 1989, 341, 225;

(b) Trost, B. M.; Fettes, A.; Shireman, B. T. J. Am. Chem. Soc. 2004, 126, 2660;

(c) Casey, C. P.; Martins, S. C.; Fagan, M. A. J. Am. Chem. Soc. 2004, 126, 5585;

(d) Chan, V. S.; Chiu, M.; Bergman, R. G.; Toste, F. D. J. Am. Chem. Soc. 2009, 131, 6021.

[4] For selected examples for control with additive, see: (a) Lutz, F.; Igarashi, T.; Kawasaki, T.; Soai, K. J. Am. Chem. Soc. 2005, 127, 12206;

(b) Lutz, F.; Igarashi, T.; Kinoshita, T.; Asahina, M.; Tsukiyama, K.; Kawasaki, T.; Soai, K. J. Am. Chem. Soc. 2008, 130, 2956;

(c) Blackmond, D. G.; Moran, A.; Hughes, M.; Armstrong, A. J. Am. Chem. Soc. 2010, 132, 7598;

(d) Tian, X.; Cassani, C.; Liu, Y.; Moran, A.; Urakawa, A.; Galzerano, P.; Arceo, E.; Melchiorre, P. J. Am. Chem. Soc. 2011, 133, 17934;

(e) Moteki, S. A.; Han, J.; Arimitsu, S.; Akakura, M.; Nakayama, K.; Maruoka, K. Angew. Chem., Int. Ed. 2012, 51, 1187;

(f) Feng, X.; Zhou, Z.; Zhou, R.; Zhou, Q.-Q.; Lin, L.; Chen, Y.-C. J. Am. Chem. Soc. 2012, 134, 19942.

[5] For selected examples of control with different center metals: (a) Spangler, K. Y.; Wolf, C. Org. Lett. 2009, 11, 4724;

(b) Nojiri, A.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2009, 131, 3779.

(c) Kim, H. Y.; Li, J.-Y.; Kim, S.; Oh, K. J. Am. Chem. Soc. 2011, 133, 20750;

(d) Liu, Y.; Shang, D.; Zhou, X.; Zhu, Y.; Lin, L.; Liu, X.; Feng, X. Org. Lett. 2010, 12, 180;

(e) Wang, Z.; Yang, Z.; Chen, D.; Liu, X.; Lin, L.; Feng, X. Angew. Chem., Int. Ed. 2011, 50, 4928;

(f) Lu, G.; Yoshino, T.; Morimoto, H.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed. 2011, 50, 4382.

[6] (a) Hamilton, G. L.; Kang, E. J.; Mba, M.; Toste, F. D. Science 2007, 317, 496;

(b) Ding, Z.-Y.; Chen, F.; Qin, J.; He, Y.-M.; Fan, Q.-H. Angew. Chem., Int. Ed. 2012, 51, 5706;

(c) Martínez- Castanñeda, A.; Rodríguesz-Solla, H.; Concellón, C.; del Amo, V. J. Org. Chem. 2012, 77, 10375.

[7] For recent reviews on asymmetric Friedel-Crafts reactions, see: (a) You, S.-L.; Cai, Q.; Zeng, M. Chem. Soc. Rev. 2009, 38, 2190;

(b) Poulsen, T. B.; Jørgensen, K. A. Chem. Rev. 2008, 108, 2903;

(c) Bandini, M.; Melloni, A.; Umani-Ronchi, A. Angew. Chem., Int. Ed. 2004, 43, 550;

(d) Bandini, M.; Eichholzer, A. Angew. Chem., Int. Ed. 2009, 48, 9608;

(e) Terrasson, V.; de Figueiredo, R. M.; Campagne, J. M. Eur. J. Org. Chem. 2010, 2635;

(f) He, Z.; Huang, Y.; Verpoort, F. Acta Chim. Sinica 2013, 71, 700. (何展荣, 黄毅勇, Verpoort, F. 化学学报, 2013, 71, 700).

(g) Sheng, Y.-F.; Zhang, A.-J.; Zheng, X.-J.; You, S.-L. 2008, 28, 605; For a recent example for chiral phosphoric acid catalyzed asymmetric Friedel-Crafts reaction, see:

(h) Zeng, M.; Zhang, W.; You, S.-L. Chin. J. Chem. 2012, 30, 2625.

[8] For reviews on chiral phosphoric acid, see: (a) Akiyama, T.; Itoh, J.; Fuchibe, K. Adv. Synth. Catal. 2006, 348, 999;

(b) Akiyama, T. Chem. Rev. 2007, 107, 5744;

(c) Yu, J.; Shi, F.; Gong, L.-Z. Acc. Chem. Res. 2011, 44, 1156;

(d) Rueping, M.; Kuenkel, A.; Atodiresei, L. Chem. Soc. Rev. 2011, 40, 4539;

(e) Su, Y.; Shi, F. Chin. J. Org. Chem. 2010, 30, 486. (苏亚军, 史福强, 有机化学, 2010, 30, 486).

[9] For reviews on chiral phosphoric acid and metal combined catalysis, see: (a) Rueping, M.; Koenigs, R. M.; Atodiresei, I. Chem. Eur. J. 2010, 16, 9350;

(b) Phipps, R. J.; Hamilton, G. L.; Toste, F. D. Nat. Chem. 2012, 4, 603;

(c) Mahlau, M.; List, B. Angew. Chem., Int. Ed. 2013, 52, 518;

(d) Brak, K.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2013, 52, 534;

(e) Wu, X.; Li, M.; Gong, L.-Z. Acta Chim. Sinica 2013, 71, 1091. (吴祥, 李名丽, 龚流柱, 化学学报, 2013, 71，1091); For a review on chiral phosphate salts catalysis, see:

(f) Yamashita, Y.; Tsubogo, T.; Kobayashi, S. Chem. Sci. 2012, 3, 967.

[10] For a review on asymmetric binary-acid catalysis, see: Lv, J.; Luo, S. Chem. Commun. 2013, 49, 847.

[11] (a) Lv, J.; Li, X.; Zhang, L.; Luo, S.; Cheng, J.-P. Org. Lett. 2010, 12, 1096;

(b) Lv, J.; Zhang, L.; Zhou, Y.; Nie, Z.; Luo, S.; Cheng, J.-P. Angew. Chem., Int. Ed. 2011, 50, 6610;

(c) Lv, J.; Zhang, L.; Hu, S.; Cheng, J.-P.; Luo, S. Chem. Eur. J. 2012, 18, 799;

(d) Lv, J.; Zhong, X.; Luo, S.; Cheng, J.-P. Acta Chim. Sinica 2012, 70, 1518.(吕健, 钟兴仁, 程津培, 罗三中, 化学学报, 2012, 70, 1518);

(e) Chen, L.; Zhang, L.; Lv, J.; Cheng, J.-P.; Luo, S. Chem. Eur. J. 2012, 18, 8891;

(f) Zhang, L.; Chen, L.; Lv, J.; Cheng, J.-P.; Luo, S. Chem. Asian J. 2012, 7, 2569;

(g) Lv, J.; Zhang, L.; Cheng, J.-P.; Luo, S. Angew. Chem., Int. Ed. 2013, 52, 9786.

[12] (a) Huang, J.-M.; Wong, C.-M.; Xu, F.-X.; Loh, T.-P. Tetrahedron Lett. 2007, 48, 3375;

(b) Zhao, J.-F.; Zhao, Y.-J.; Loh, T.-P. Chem. Commun. 2008, 1353;

(c) Zhao, Y.-J.; Tan, L.-J. S.; Li, B.; Li, S.-M.; Loh, T.-P. Chem. Commun. 2009, 3738.

[1]	鱼章龙, 李忠良, 杨昌江, 顾强帅, 刘心元. 铜催化的二醇类化合物对映选择性去对称化反应研究进展^★[J]. 化学学报, 2023, 81(8): 955-966.
[2]	杨爽, 王宁宜, 杭青青, 张宇辰, 石枫. 邻羟基苯基取代的对亚甲基苯醌参与的催化不对称反应研究进展^★[J]. 化学学报, 2023, 81(7): 793-808.
[3]	王瑞祥, 赵庆如, 顾庆, 游书力. 金/铱接力催化炔基酰胺环化/不对称烯丙基苄基化串联反应^★[J]. 化学学报, 2023, 81(5): 431-434.
[4]	高杨, 张学鑫, 余金生, 周剑. α-手性三级叠氮化合物的不对称催化合成新进展^★[J]. 化学学报, 2023, 81(11): 1590-1608.
[5]	孟庆端, 韩佳宏, 潘一骁, 郝伟, 范青华. C₁-对称手性氮杂环卡宾(NHC)配体的不对称合成及其催化性能研究^★[J]. 化学学报, 2023, 81(10): 1271-1279.
[6]	张崃, 肖检, 王雅雯, 彭羽. 苯酚(醌)与烯烃的不对称[3+2]环化反应: 手性二氢苯并呋喃的合成进展[J]. 化学学报, 2022, 80(8): 1152-1164.
[7]	马进越, 黄露霏, 周宝文, 姚琳. 无机手性纳米结构的可控构筑及其催化研究进展[J]. 化学学报, 2022, 80(11): 1507-1523.
[8]	赵庆如, 蒋茹, 游书力. 铱催化串联不对称烯丙基取代/双键异构化构建轴手性化合物[J]. 化学学报, 2021, 79(9): 1107-1112.
[9]	穆博帅, 张志豪, 武文彪, 余金生, 周剑. 手性1,2-二氢吡啶化合物的合成研究进展[J]. 化学学报, 2021, 79(6): 685-693.
[10]	李翼, 徐明华. 不对称Petasis反应在手性胺类化合物合成中的应用[J]. 化学学报, 2021, 79(11): 1345-1359.
[11]	朱仁义, 廖奎, 余金生, 周剑. P-手性膦氧化物的不对称催化合成研究进展[J]. 化学学报, 2020, 78(3): 193-216.
[12]	王强, 顾庆, 游书力. 过渡金属催化不对称C—H键官能团化反应构建轴手性联芳基化合物研究进展[J]. 化学学报, 2019, 77(8): 690-704.
[13]	蔡倩, 马浩文. 手性高价碘试剂的发展及展望[J]. 化学学报, 2019, 77(3): 213-230.
[14]	周远春, 周志, 杜玮, 陈应春. HOMO活化的2-吡喃酮与2,5-二烯酮反电子需求的不对称Diels-Alder反应[J]. 化学学报, 2018, 76(5): 382-386.
[15]	李树森, 王剑波. 不对称三氟甲硫基化反应研究进展[J]. 化学学报, 2018, 76(12): 913-924.