咪唑离子官能化的HG-II型手性钌催化剂的制备及其催化的不对称烯烃复分解反应

doi:10.6023/cjoc202111029

有机化学 ›› 2022, Vol. 42 ›› Issue (6): 1713-1721.DOI: 10.6023/cjoc202111029 上一篇下一篇

研究论文

咪唑离子官能化的HG-II型手性钌催化剂的制备及其催化的不对称烯烃复分解反应

李涛^a, 刘艺^a, 白雪^a, 周遵军^a, 左鹏^a, 麻妙锋^a, 仲崇民^a^,^*(), 左亚杰^b^,^*()

a 西北农林科技大学化学与药学院陕西杨凌 712100
b 西北农林科技大学资源环境学院陕西杨凌 712100

收稿日期:2021-11-09 修回日期:2022-01-10 发布日期:2022-03-21
通讯作者: 仲崇民, 左亚杰
基金资助:
国家自然科学基金(21673183)

Preparation of Imidazolium Ion Functionalized HG-II Chiral Ruthenium Catalysts and Their Catalytic Performance in Asymmetric Olefin Metathesis

Tao Li^a, Yi Liu^a, Xue Bai^a, Zunjun Zhou^a, Peng Zuo^a, Miaofeng Ma^a, Chong-Min Zhong^a(), Ya-Jie Zuo^b()

a College of Chemistry and Pharmacy, Northwest Agriculture and Forestry University, Yangling, Shannxi 712100
b College of Natural Resources and Environment, Northwest Agriculture and Forestry University, Yangling, Shannxi 712100

Received:2021-11-09 Revised:2022-01-10 Published:2022-03-21
Contact: Chong-Min Zhong, Ya-Jie Zuo
Supported by:
National Natural Science Foundation of China(21673183)

文章分享

1. 221713S.pdf(2227KB)

摘要/Abstract

钌催化的烯烃复分解反应的产率以及立体选择性主要决定于配体的性质. 在手性HG-II型催化剂的Hoveyda配体上修饰一个咪唑离子官能团, 并考察了所得催化剂在不对称关环复分解(ARCM)和不对称开环交叉烯烃复分解(AROCM)反应中的活性和立体选择性. 结果表明, 在ARCM反应中离子官能团的修饰与否对反应结果没有显著影响; 在AROCM反应中, 离子官能团的修饰对催化剂的活性没有影响, 但对某些产物的E/Z选择性和ee值有较明显的影响. 离子修饰使有些底物生成产物的E/Z值和ee值都有提高, 但对另一些底物则没有显著影响. 因此, 在AROCM反应中可以考虑用咪唑修饰的Hoveyda配体作为提高反应立体选择性的一个手段.

关键词: 咪唑离子, GH-II型钌催化剂, 手性钌催化剂, 不对称开环交叉烯烃复分解, Hoveyda配体

The yield and stereoselectivity of the ruthenium-catalyzed olefin metathesis reaction are mainly determined by the nature of the ligands. In this study, two chiral HG-II ruthenium catalysts with imidazolium ion functionalized Hoveyda ligands were prepared, and their activity and stereoselectivity in the symmetric ring-closure metathesis (ARCM) and asymmetric ring-opening cross-olefin metathesis (AROCM) reactions were investigated. The results show that the modification of the Hoveyda ligands by ionic functional group produced no significant effect on ARCM reaction. For AROCM reaction, the ionic modification of the Hoveyda ligands shows an obvious improvment on both the E/Z selectivity and ee value for some products. Therefore, in the AROCM reaction, the Hoveyda ligands modified with imidazolium ion can be considered as a means to improve the stereoselectivity of the reaction.

Key words: imidazolium ion, GH-II ruthenium catalysts, chiral ruthenium catalysts, asymmetric ring opening cross metathesis, Hoveyda ligands

引用此文

李涛, 刘艺, 白雪, 周遵军, 左鹏, 麻妙锋, 仲崇民, 左亚杰. 咪唑离子官能化的HG-II型手性钌催化剂的制备及其催化的不对称烯烃复分解反应[J]. 有机化学, 2022, 42(6): 1713-1721.

Tao Li, Yi Liu, Xue Bai, Zunjun Zhou, Peng Zuo, Miaofeng Ma, Chong-Min Zhong, Ya-Jie Zuo. Preparation of Imidazolium Ion Functionalized HG-II Chiral Ruthenium Catalysts and Their Catalytic Performance in Asymmetric Olefin Metathesis[J]. Chinese Journal of Organic Chemistry, 2022, 42(6): 1713-1721.

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

分享此文

图/表 10

图1. 一些典型的钌复分解催化剂

Figure 1. Some typical ruthenium metathesis catalysts

图2. 本工作合成的HG-II型手性钌配合物

Figure 2. HG-II type ruthenium complexes synthesized in this work

图式1. 手性咪唑盐13的合成

Scheme 1. Synthesis of chiral imidazolinium 13

图式2. 咪唑盐修饰的手性催化剂1的合成

Scheme 2. Synthesis of imidazolium-tagged chiral catalyst 1

图式3. 催化剂3的合成

Scheme 3. Synthesis of chiral catalyst 3

图式4. 手性催化剂2和4的合成

Scheme 4. Synthesis of chiral catalysts 2 and 4

Entry	Substrate	Product	Catalyst	ee^b/%	Yield^c/%
1	17a	18a	3	11	98
2	17a	18a	1	11	98
3	17b	18b	3	5	94
4	17b	18b	1	3	93
5	17a	18a	4	35	95
6	17a	18a	2	35	96
7	17b	18b	4	40	95
8	17b	18b	2	39	95

表1. 催化剂1~4催化的不对称三烯关环复分解反应a

Table 1. Asymmetric ring-closing metathesis catalyzed by 1~4

图3. 催化剂1和2在ARCM反应中不对称诱导的差异

Figure 3. Difference of asymmetric induction for 1 and 2 catalyzed ARCM reaction

Entry	Catalyst	ee^b/%	Yield^c/%	Z∶E^d
1	3	11	98	5∶95
2	1	7	98	23∶77
3	4	21	97	26∶74
4	2	22	97	11∶89
5	3	9	96	5∶95
6	1	15	92	3∶97
7	4	9	95	5∶95
8	2	19	97	2∶98
9	3	65	97	3∶97
10	1	45	98	2∶98
11	4	27	96	2∶98
12	2	50	95	2∶98
13	3	7	97	17∶83
14	1	7	98	17∶83
15	4	27	98	13∶87
16	2	25	96	10∶90

表2. 手性钌催化剂1~4催化的不对称开环交叉复分解反应a

Table 2. Asymmetric ring-opening cross metathesis catalyzed by 1~4

图式5. 催化剂3(或4)与1(或2)在AROCM反应中催化剂中间体的差异

Scheme 5. Difference of catalytic intermediates for 3 (or 4) and 1 (or 2) catalyzed AROCM reaction

参考文献 29

[1]	Kress, S.; Blechert, S. Chem. Soc. Rev. 2012, 41, 4389. doi: 10.1039/c2cs15348c
[2]	Hoveyda, A. H.; Malcolmson, S. J.; Meek, S. J.; Zhugralin, A. R. Angew. Chem., Int. Ed. 2010, 49, 34. doi: 10.1002/anie.200904491
[3]	Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett. 2001, 3, 3225. pmid: 11574037
[4]	Funk, T. W.; Berlin, J. M.; Grubbs, R. H. J. Am. Chem. Soc. 2006, 128, 1840. doi: 10.1021/ja055994d
[5]	Berlin, J. M.; Goldberg, S. D.; Grubbs, R. H. Angew. Chem., Int. Ed. 2006, 45, 7591. doi: 10.1002/anie.200602469
[6]	Hartung, J.; Dornan, P. K.; Grubbs, R. H. J. Am. Chem. Soc. 2014, 136, 13029. doi: 10.1021/ja506611k pmid: 25137310
[7]	Van Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 4954. pmid: 11982348
[8]	Van Veldhuizen, J. J.; Gillingham, D. G.; Garber, S. B.; Kataoka, O.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 12502. pmid: 14531694
[9]	Van Veldhuizen, J. J.; Campbell, J. E.; Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 6877. pmid: 15869311
[10]	Cortez, G. A.; Baxter, C. A.; Schrock, R. R.; Hoveyda, A. H. Org. Lett. 2007, 9, 2871. pmid: 17585770
[11]	Giudici, R. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2007, 129, 3824. doi: 10.1021/ja070187v
[12]	Fournier, P.-A.; Collins, S. K. Organometallics 2007, 26, 2945. doi: 10.1021/om700312c
[13]	Fournier, P.-A.; Savoie, J.; Stenne, B.; Bédard, M.; Grandbois, A.; Collins, S. K. Chem. Eur. J. 2008, 14, 8690. doi: 10.1002/chem.200800642
[14]	Grandbois, A.; Collins, S. K. Chem. Eur. J. 2008, 14, 9323. doi: 10.1002/chem.200801033
[15]	Savoie, J.; Stenne, B.; Collins, S. K. Adv. Synth. Catal. 2009, 351, 1826. doi: 10.1002/adsc.200900269
[16]	Stenne, B.; Timperio, J.; Savoie, J.; Dudding, T.; Collins, S. K. Org. Lett. 2010, 12, 2032. doi: 10.1021/ol100511d pmid: 20337494
[17]	Paradiso, V.; Bertolasi, V.; Costabile, C.; Grisi, F. Dalton Trans. 2016, 45, 561. doi: 10.1039/C5DT03758A
[18]	Paradiso, V.; Bertolasi, V.; Costabile, C.; Caruso, T.; Dąbrowski, M.; Grela, K.; Grisi, F. Organometallics 2017, 36, 3692. doi: 10.1021/acs.organomet.7b00488
[19]	Ambrosio, C.; Paradiso, V.; Costabile, C.; Bertolasi, V.; Caruso, T.; Grisi, F. Dalton Trans. 2018, 47, 6615. doi: 10.1039/c8dt00619a pmid: 29701229
[20]	Grisi, F.; Costabile, C.; Gallo, E.; Mariconda, A.; Tedesco, C.; Longo, P. Organometallics 2008, 27, 4649. doi: 10.1021/om800459y
[21]	Tiede, S.; Berger, A.; Schlesiger, D.; Rost, D.; Lühl, A.; Blechert, S. Angew. Chem., Int. Ed. 2010, 49, 3972.
[22]	Kannenberg, A.; Rost, D.; Eibauer, S.; Tiede, S.; Blechert, S. Angew. Chem., Int. Ed. 2011, 50, 3299.
[23]	Ivry, E.; Ben-Asuly, A.; Goldberg, I.; Lemcoff, N. G. Chem. Commun. 2015, 51, 3870. doi: 10.1039/C5CC00052A
[24]	Chen, S.-W.; Zhang, Z.-C.; Ma, M.; Zhong, C.-M.; Lee, S.-G. Org. Lett. 2014, 16, 4969.
[25]	Chen, S.-W.; Zhang, Z.-C.; Zhai, N.-N.; Zhong, C.-M.; Lee, S.-G. Tetrahedron 2015, 71, 648. doi: 10.1016/j.tet.2014.12.024
[26]	Chen, X.-L.; Li, X.-Y.; Li, S.-S.; Bai, X.; Li, T.; Goud, E. Y.; Zhong, C.-M.; Zuo, Y.-J. Russ. J. Gen. Chem. 2020, 90, 2163. doi: 10.1134/S1070363220110237
[27]	For the synthesis of the triflate analog of chiral imidazolinium salt 13, see: Zhang, J.; Su, X.; Fu, J.; Shi, M. Chem. Commun. 2011, 47, 12541. doi: 10.1039/c1cc15609h
[28]	Costabile, C.; Cavallo, L. J. Am. Chem. Soc. 2004, 126, 9592. pmid: 15291563
[29]	June, S. L.; Laleh, T.; James, A. G.; Curtis, M.; Arnold, L. R.; Linda, H. D. Chem. Eur. J. 2013, 19, 6374. doi: 10.1002/chem.201204275

咪唑离子官能化的HG-II型手性钌催化剂的制备及其催化的不对称烯烃复分解反应

Preparation of Imidazolium Ion Functionalized HG-II Chiral Ruthenium Catalysts and Their Catalytic Performance in Asymmetric Olefin Metathesis

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 10

参考文献 29

相关文章 0

编辑推荐

相关统计

本文评价