(4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(II) Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions

doi:10.6023/cjoc202311029

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (7): 2315-2332.DOI: 10.6023/cjoc202311029 Previous Articles Next Articles

ARTICLES

(4S,4'S)-2,2'-(4,6-二苯并呋喃二基)双[4,5-二氢-4-苯基噁唑]-镍(II)配合物催化高对映选择性氰亚胺的环加成反应

曹茜娴, 由君^*(), 刘其业, 刘波, 喻艳超, 武文菊^*()

哈尔滨理工大学材料科学与化学工程学院绿色化工技术黑龙江省高校重点实验室哈尔滨 150080

收稿日期:2023-11-27 修回日期:2024-02-27 发布日期:2024-03-28
基金资助:
国家自然科学基金(22278098); 国家自然科学基金(21908034); 国家自然科学基金(22008045); 黑龙江省自然科学基金(LH2021H001); 黑龙江省自然科学基金(LH2023B013)

(4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(II) Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions

Xixian Cao, Jun You(), Qiye Liu, Bo Liu, Yanchao Yu, Wenju Wu()

Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Materials Science and Chemical Engineering, Harbin University of Science and Technology, Harbin 150080

Received:2023-11-27 Revised:2024-02-27 Published:2024-03-28
Contact: * E-mail: youjunjun@126.com;wuwenju1017@163.com
Supported by:
National Natural Science Foundation of China ((22278098); National Natural Science Foundation of China ((21908034); National Natural Science Foundation of China ((22008045); Natural Science Foundation of Heilongjiang Province(LH2021H001); Natural Science Foundation of Heilongjiang Province(LH2023B013)

1. .pdf(18676KB)

Abstract

The Ni(II)-chiral (4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole] (DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented. This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cycloadducts bearing one or two contiguous stereocenters in good yields (up to 97% yield) with high regioselectivities (100%) and enantioselectivities (up to 97.5% ee). Following that, chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process, additionally, toward five kinds of derivatization reactions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.

Key words: (4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole] (DBFOX/Ph), 1,3-dipolar cycloaddition, nitrile imines, N-α,β-unsaturated acylpyrazole, enantioselectivity, electronic circular dichroism (ECD) calculation

Cite this article

Xixian Cao, Jun You, Qiye Liu, Bo Liu, Yanchao Yu, Wenju Wu. (4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(II) Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2315-2332.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 48

[1]	Poulsen, P. H.; Li, Y.; Lauridsen, V. H.; Jørgensen, D. K. B.; Palazzo, T. A.; Meazza, M.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2018, 57, 10661.
[2]	Wang, K.; Xiao, Y. Chirality 2021, 33, 424.
[3]	Wang, M.; Zhang, Z.; Zhang, W. Acc. Chem. Res. 2022, 55, 2708.
[4]	Hilpert, L. J.; Sieger, S. V.; Haydl, A. M.; Breit, B. Angew. Chem., Int. Ed. 2019, 131, 3416.
[5]	Zengeya, T. T.; Garlick, J. M.; Kulkarni, R. A.; Miley, M.; Roberts, A. M.; Yang, Y.; Crooks, D. R.; Sourbier, C.; Linehan, W. M.; Meier, J. L. J. Am. Chem. Soc. 2016, 138, 15813. pmid: 27960310
[6]	Nunes, R. C.; Ribeiro, C. J. A.; Monteiro, Â.; Rodrigues, C. M. P.; Amaral, J. D.; Santos, M. M. M. Eur. J. Med. Chem. 2017, 139, 168. doi: S0223-5234(17)30579-2 pmid: 28800455
[7]	Ahsan, M. J.; Ali, A.; Ali, A.; Thiriveedhi, A.; Bakht, M. A.; Yusuf, M.; Salahuddin; Afzal, O.; Altamimi, A. S. A. ACS Omega 2022, 7, 38207.
[8]	Fahrni, C. J.; Yang, L.; VanDerveer, D. G. J. Am. Chem. Soc. 2003, 125, 3799.
[9]	Chen, J. R.; Dong, W. R.; Candy, M.; Pan, F. F.; Jörres, M.; Bolm, C. J. Am. Chem. Soc. 2012, 134, 6924.
[10]	Thomson, C. J.; Barber, D. M.; Dixon, D. J. Angew. Chem., Int. Ed. 2019, 131, 2491.
[11]	Yang, C. J.; Zhang, C.; Gu, Q. S.; Fang, J. H.; Su, X. L.; Ye, L.; Sun, Y.; Tian, Y.; Li, Z. L.; Liu, X. Y. Nat. Catal. 2020, 3, 539.
[12]	Hu, F.; Zhang, H.; Chu, Y.; Hui, X. P. Org. Chem. Front. 2022, 9, 2734.
[13]	Matiadis, D. Adv. Synth. Catal. 2023, 365, 1934.
[14]	Yamashita, Y.; Kobayashi, S. J. Am. Chem. Soc. 2004, 126, 11279. pmid: 15355109
[15]	Wang, C.; Wen, D.; Chen, H.; Deng, Y.; Liu, X.; Liu, X.; Wang, L.; Gao, F.; Guo, Y.; Sun, M.; Wang, K.; Yan, W. Org. Biomol. Chem. 2019, 17, 5514. doi: 10.1039/c9ob00720b pmid: 31115424
[16]	Hashimoto, T.; Takiguchi, Y.; Maruoka, K. J. Am. Chem. Soc. 2013, 135, 11473. doi: 10.1021/ja405444c pmid: 23869712
[17]	Zhang, D. Y.; Shao, L.; Xu, J.; Hu, X. P. ACS Catal. 2015, 5, 5026.
[18]	Deepthi, A.; Acharjee, N.; Sruthi, S. L.; Meenakshy, C. B. Tetrahedron 2022, 116, 132812.
[19]	Song, L.; Lai, Y.; Li, H.; Ding, J.; Yao, H.; Su, Q.; Huang, B.; Ouyang, M. A.; Tong, R. J. Org. Chem. 2022, 87, 10550.
[20]	Sibi, M. P.; Stanley, L. M.; Jasperse, C. P. J. Am. Chem. Soc. 2005, 127, 8276.
[21]	Wang, G.; Liu, X.; Huang, T.; Kuang, Y.; Lin, L.; Feng, X. Org. Lett. 2013, 15, 76.
[22]	Gerten, A. L.; Slade, M. C.; Pugh, K. M.; Stanley, L. M. Org. Biomol. Chem. 2013, 11, 7834.
[23]	Pellissier, H. Tetrahedron 2007, 63, 3235.
[24]	Hashimoto, T.; Maruoka, K. Chem. Rev. 2015, 115, 5366. doi: 10.1021/cr5007182 pmid: 25961125
[25]	Nishiura, Y.; Gonzalez, K. J.; Cusumano, A. Q.; Stoltz, B. M. Org. Lett. 2023, 25, 6469.
[26]	Wu, D.; Qiu, J.; Li, C.; Yuan, L.; Yin, H.; Chen, F. X. J. Org. Chem. 2019, 85, 934.
[27]	Wang, C. J.; Sun, J.; Zhou, W.; Xue, J.; Ren, B. T. Zhang, G. Y. Mei, Y. L. Deng, Q. H. Org. Lett. 2019, 21, 7315.
[28]	Shen, X.; Li, Y.; Wen, Z.; Cao, S.; Hou, X.; Gong, L. Chem. Sci. 2018, 9, 4562.
[29]	Itoh, K.; Sibi, M. P. Org. Biomol. Chem. 2018, 16, 5551.
[30]	Kanemasa, S.; Oderaotoshi, Y.; Tanaka, J.; Wada, E. J. Am. Chem. Soc. 1998, 120, 12355.
[31]	Yang, X.; Cheng, F.; Kou, Y. D.; Pang, S.; Shen, Y. C.; Huang, Y. Y.; Shibata, N. Angew. Chem., Int. Ed. 2017, 129, 1532.
[32]	Liu, X.; Li, M.; You, J.; Liu, B. Chin. J. Org. Chem. 2017, 37, 86. (in Chinese)
	(刘迅绅, 李美美, 由君, 刘波, 有机化学, 2017, 37, 86.)
[33]	Ono, F.; Ohta, Y.; Hasegawa, M.; Kanemasa, S. Tetrahedron Lett. 2009, 50, 2111.
[34]	Zhang, J.; Liu, X.; Wang, R. Chem- Eur. J. 2014, 20, 4911.
[35]	Zhang, Y.; Liao, Y.; Liu, X.; Yao, Q.; Zhou, Y.; Lin, L.; Feng, X. Chem.-Eur. J. 2016, 22, 15119. doi: 10.1002/chem.201603056 pmid: 27576747
[36]	Yao, Q.; Wang, Z.; Zhang, Y.; Liu, X.; Lin, L.; Feng, X. J. Org. Chem. 2015, 80, 5704.
[37]	Liu, X. H.; Ruan, B. F.; Li, J.; Chen, F. H.; Song, B. A.; Zhu, H. L.; Bhadury, P. S.; Zhao, J. Mini-Rev. Med. Chem. 2011, 11, 771.
[38]	Küçükgüzel, Ş. G.; Şenkardeş, S. Eur. J. Med. Chem. 2015, 97, 786. doi: 10.1016/j.ejmech.2014.11.059 pmid: 25555743
[39]	Liu, H.; Jia, H.; Wang, B.; Xiao, Y.; Guo, H. Org. Lett. 2017, 19, 4714.
[40]	Wang, Y.; Zhang, P.; Di, X.; Dai, Q.; Zhang, Z. M.; Zhang, J. Angew. Chem., Int. Ed. 2017, 129, 16121.
[41]	Lu, T. Molclus program, Version 1. 5,
[42]	Stewart, J. J. P. J. Comput.-Aided Mol. Des. 1990, 4, 1.
[43]	Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864.
[44]	Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133.
[45]	Grimme, S.; Antony. J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104.
[46]	Petersson, G. A.; Bennett, A.; Tensfeldt, T. G; Al-Laham, M. A.; Shirley, W. A.; Mantzaris, J. J. Chem. Phys. 1988, 89, 2193.
[47]	Weigend, F.; Ahlrichs, R. Phys. Chem. Chem. Phys. 2005, 7, 3297.
[48]	Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580.

Entry	Ligand^b	Metal salt	Solvent	Base	Yield^c/%	ee^d/%
1	L1	Ni(ClO₄)₂	DCM	DIPEA	88	5.0
2	L2	Ni(ClO₄)₂	DCM	DIPEA	90	7.0
3	L3	Ni(ClO₄)₂	DCM	DIPEA	91	3.0
4	L4	Ni(ClO₄)₂	DCM	DIPEA	88	13.1
5	L5	Ni(ClO₄)₂	DCM	DIPEA	90	5.1
6	L6	Ni(ClO₄)₂	DCM	DIPEA	93	62.0
7	L7	Ni(ClO₄)₂	DCM	DIPEA	90	6.0
8	L8	Ni(ClO₄)₂	DCM	DIPEA	90	7.1
9	L6	Mg(NTf₂)₂	DCM	DIPEA	92	38.3
10	L6	Cu(CH₃CN)₄•PF₆	DCM	DIPEA	90	42.2
11	L6	Sc(OTf)₃	DCM	DIPEA	87	37.0
12	L6	Zn(OTf)₂	DCM	DIPEA	89	32.1
13	L6	Ni(ClO₄)₂	Et₂O	DIPEA	91	46.2
14	L6	Ni(ClO₄)₂	Toluene	DIPEA	92	39.1
15	L6	Ni(ClO₄)₂	DCE	DIPEA	95	82.0
16	L6	Ni(ClO₄)₂	THF	DIPEA	93	43.3
17	L6	Ni(ClO₄)₂	DCE	NMM	40	46.0
18	L6	Ni(ClO₄)₂	DCE	Pyridine	10	0
19	L6	Ni(ClO₄)₂	DCE	DBU	0	0

Entry	Ligand^b	Metal salt	Solvent	Base	Yield^c/%	ee^d/%
1	L1	Ni(ClO₄)₂	DCM	DIPEA	88	5.0
2	L2	Ni(ClO₄)₂	DCM	DIPEA	90	7.0
3	L3	Ni(ClO₄)₂	DCM	DIPEA	91	3.0
4	L4	Ni(ClO₄)₂	DCM	DIPEA	88	13.1
5	L5	Ni(ClO₄)₂	DCM	DIPEA	90	5.1
6	L6	Ni(ClO₄)₂	DCM	DIPEA	93	62.0
7	L7	Ni(ClO₄)₂	DCM	DIPEA	90	6.0
8	L8	Ni(ClO₄)₂	DCM	DIPEA	90	7.1
9	L6	Mg(NTf₂)₂	DCM	DIPEA	92	38.3
10	L6	Cu(CH₃CN)₄•PF₆	DCM	DIPEA	90	42.2
11	L6	Sc(OTf)₃	DCM	DIPEA	87	37.0
12	L6	Zn(OTf)₂	DCM	DIPEA	89	32.1
13	L6	Ni(ClO₄)₂	Et₂O	DIPEA	91	46.2
14	L6	Ni(ClO₄)₂	Toluene	DIPEA	92	39.1
15	L6	Ni(ClO₄)₂	DCE	DIPEA	95	82.0
16	L6	Ni(ClO₄)₂	THF	DIPEA	93	43.3
17	L6	Ni(ClO₄)₂	DCE	NMM	40	46.0
18	L6	Ni(ClO₄)₂	DCE	Pyridine	10	0
19	L6	Ni(ClO₄)₂	DCE	DBU	0	0

Entry	Temp./℃	Amount^b/mol%	Yield/%	ee/%
1	10	6	94	83.7
2	30	6	95	82.0
3	40	6	90	83.0
4	50	6	91	83.8
5	65	6	82	42.7
6	0	6	95	89.0
7	–10	6	90	82.5
8	–30	6	92	71.1
9	–40	6	80	55.1
10	–50	6	75	40.5
11	–65	6	20	12.0
12	0	8	95	92.0
13	0	10	97	97.5
14	0	12	96	97.6

Entry	Temp./℃	Amount^b/mol%	Yield/%	ee/%
1	10	6	94	83.7
2	30	6	95	82.0
3	40	6	90	83.0
4	50	6	91	83.8
5	65	6	82	42.7
6	0	6	95	89.0
7	–10	6	90	82.5
8	–30	6	92	71.1
9	–40	6	80	55.1
10	–50	6	75	40.5
11	–65	6	20	12.0
12	0	8	95	92.0
13	0	10	97	97.5
14	0	12	96	97.6

(4S,4'S)-2,2'-(4,6-二苯并呋喃二基)双[4,5-二氢-4-苯基噁唑]-镍(II)配合物催化高对映选择性氰亚胺的环加成反应

(4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(II) Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 48

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Feifan Li, Kang Yu, Chuanzhi Ni, Yuanyuan Zhu, Jie Zeng, Shuangxi Gu. Chiral Fluorescent Probes for Determination of Both Concentration and Enantiomeric Composition of Amino Acids [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1862-1869.
[2]	Chun Gao, Xin Liu, Minghui Wang, Shuxian Liu, Tingting Zhu, Yikang Zhang, Erjun Hao, Qiliang Yang. Advances in Asymmetric Electrochemical Synthesis [J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 673-727.
[3]	Hu Ma, Danfeng Huang, Kehu Wang, Duoduo Tang, Yang Feng, Yuanyuan Reng, Junjiao Wang, Yulai Hu. Synthesis of 3-Trifluoromethylpyrazole Derivatives [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3257-3267.
[4]	Hui Yan, Man Zhang, Lin Li, Teng Hu, Wulin Yang. Advances in the Catalytic Asymmetric Synthesis of Chiral Spiroketals [J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3640-3657.
[5]	Yuanyuan Ping, Haixia Song, Wangqing Kong. Recent Advances in Ni-Catalyzed Asymmetric Reductive Difunctionalization of Alkenes [J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3302-3321.
[6]	Quancheng Li, Lan Jiang, Rui Bai, Yongkang Han, Zhengning Li. Progress in the Synthesis of 3-Substituted Phthaides [J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3390-3399.
[7]	Lulu Yu, Qunshan Ding, Chuanjun Song, Junbiao Chang. Enantioselective Total Synthesis of (–)-Angustureine [J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2507-2510.
[8]	Chenchen Zou, Changhao Niu, Xinyu Liu, Chun Zhang. Recent Advances about Protoboration of Conjugated Dienes [J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4240-4254.
[9]	Zhang Lu, Liu Aiqin, Liu Huazheng, Wan Renzhong, Sun Shutao, Liu Lei. Catalytic Asymmetric Synthesis of β,γ-Alkynyl α-Amino Esters via Chemo- and Enantio-selective Transfer Hydrogenation [J]. Chinese Journal of Organic Chemistry, 2020, 40(9): 2904-2911.
[10]	Wu Lizuo, Zhang Fengyuan, Zhang Zhentao, Shang Lei, Liu Yu. Ming-Phos/Copper(I)-Catalyzed Asymmetric Intermolecular[3+2] Cycloaddition of Azomethine Ylides with Trifluoromethyl Enones [J]. Chinese Journal of Organic Chemistry, 2020, 40(8): 2460-2467.
[11]	Guo Xiao, Wang Yazhou, Chen Jie, Li Gongqiang, Xia Ji-Bao. Recent Advances of CO₂ Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules [J]. Chinese Journal of Organic Chemistry, 2020, 40(8): 2208-2220.
[12]	Xu Ronghua, Yang He, Tang Wenjun. Efficient Synthesis of Chiral Drugs Facilated by P-Chiral Phosphorus Ligands [J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1409-1422.
[13]	Yao Biao, Wu Jiahao, Wang Yu, Jiang Huanfeng. Methods of Transition Metal-Catalyzed Asymmetric Oxidation [J]. Chinese Journal of Organic Chemistry, 2020, 40(10): 3044-3064.
[14]	Li Minglong, Cao Xixian, You Jun, Yu Yanchao, Wu Wenju, Liu Bo. Asymmetric 1,3-Dipolar Cycloaddition Reaction of C,N-Diarylnitrone with N-α,β-Unsaturated Acyl Compounds Catalyzed by Chiral Bisoxazoline Metal Complex [J]. Chin. J. Org. Chem., 2019, 39(6): 1642-1649.
[15]	Jiang Haiyang, Li Qiang, Qi Qingjie, Yang Chenxi, Zhang Dan. Theoretical Study on the Conjugate Addition of Asymmetric Michael Addition of trans-1-Nitro-2-phenylethylene to 2-Methylpropion-aldehyde Catalyzed by Cinchona Alkaloid Derived Primary Amine [J]. Chin. J. Org. Chem., 2018, 38(4): 825-831.