三乙胺催化的γ-羟基-α,β-不饱和酮与三氟甲基酮通过半缩酮中间体的级联反应

doi:10.6023/cjoc202010040

有机化学 ›› 2021, Vol. 41 ›› Issue (4): 1614-1621.DOI: 10.6023/cjoc202010040 上一篇下一篇

研究论文

三乙胺催化的γ-羟基-α,β-不饱和酮与三氟甲基酮通过半缩酮中间体的级联反应

马海^a, 于广浩^a, 隋峰^a, 杨米一^a, 刘丽^a, 李慧杰^a, 李峰^b^,^*(), 赵庆贺^a^,^*()

a 中国中医科学院中药研究所北京 100700
b 商丘师范学院化学化工学院药物绿色合成河南省工程实验室河南商丘 476000

收稿日期:2020-10-29 修回日期:2020-12-05 发布日期:2020-12-24
通讯作者: 李峰, 赵庆贺
作者简介:
† 共同第一作者(These authors contributed equally to this work).
基金资助:
中国中医科学院自主研发(ZZ0908028)

Triethylamine-Catalyzed Cascade Reaction of γ-Hydroxy-α,β-unsaturated Ketones with Trifluoromethyl Ketones via Hemiketal Intermediates

Hai Ma^a, Guanghao Yu^a, Feng Sui^a, Miyi Yang^a, Li Liu^a, Huijie Li^a, Feng Li^b^,^*(), Qinghe Zhao^a^,^*()

a Institute of Chinese Materia Medica, China Academy of Chinese Medical Sciences, Bejing 100700
b College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000

Received:2020-10-29 Revised:2020-12-05 Published:2020-12-24
Contact: Feng Li, Qinghe Zhao
About author:
* Corresponding authors. E-mail: qhzhao@icmm.ac.cn;
E-mail: lifeng20150720@163.com
Supported by:
Voluntary Program of China Academy of Chinese Medical Sciences(ZZ0908028)

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1. cjoc202010040辅助材料.pdf(2315KB)

摘要/Abstract

研究了三乙胺催化的γ-羟基-α,β-不饱和酮与三氟甲基酮通过半缩酮中间体的级联反应, 以高收率以及适中的非对映选择性得到了一系列产物. 在手性奎宁衍生的双功能硫脲催化剂存在下, 该反应以92%的收率以及96%的立体选择性得到目标产物.

关键词: γ-羟基-α,β-不饱和酮, 三氟甲基酮, 1,3-二噁烷衍生物, 手性硫脲

Et₃N-catalyzed cascade reaction of trifluoromethyl ketones and γ-hydroxy-α,β-unsaturated ketones via hemiketal intermediate is investigated. The adducts could be easily obtained in good to excellent yields with moderate diastereoselectivities. The reaction proceeded smoothly to give the desired product in 92% yield and with 96% ee in the presence of a glycosyl and quinidine-based bifunctional chiral thiourea catalyst.

Key words: γ-hydroxy-α,β-unsaturated ketone, trifluoromethyl ketone, 1,3-dioxolanes derivative, chiral thiourea

引用此文

马海, 于广浩, 隋峰, 杨米一, 刘丽, 李慧杰, 李峰, 赵庆贺. 三乙胺催化的γ-羟基-α,β-不饱和酮与三氟甲基酮通过半缩酮中间体的级联反应[J]. 有机化学, 2021, 41(4): 1614-1621.

Hai Ma, Guanghao Yu, Feng Sui, Miyi Yang, Li Liu, Huijie Li, Feng Li, Qinghe Zhao. Triethylamine-Catalyzed Cascade Reaction of γ-Hydroxy-α,β-unsaturated Ketones with Trifluoromethyl Ketones via Hemiketal Intermediates[J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1614-1621.

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图/表 6

Figure 1. Selected examples of chiral acetals embodied with biological and pharmacological activity

Scheme 1. Cascade reaction of γ-hydroxy-α,β-unsaturated ketones by organocatalyst

Entry	Catalyst	Solvent	T/℃	Yield^b/%	dr^c
1	E₃N	Et₂O	25	95	60∶40
2	DABCO	Et₂O	25	85	65∶35
3	DBU	Et₂O	25	82	65∶35
4	Ph₃P	Et₂O	25	—	—
5	DMAP	Et₂O	25	70	55∶45
6	Na₂CO₃	Et₂O	25	42	55∶45
7	K₂CO₃	Et₂O	25	40	55∶45
8	Et₃N	CH₂Cl₂	25	90	50∶50
9	Et₃N	PhMe	25	85	55∶45
10	Et₃N	THF	25	92	60∶40
11	Et₃N	MTBE	25	99	70∶30

Table 1. Optimization of conditionsa

Table 2. Scope of substratesa

Scheme 3. Catalytic enantioselective annulation

Scheme 4. Scaling-up experiment of the tandem cyclization

参考文献 11

[1]	(a) Royer, J. Asymmetric Synthesis of Nitrogen Heterocycles, Wiley VCH, Wienheim, 2009. pmid: 24651197
	(b) Vo, C.-V. T.; Luescher, M.U.; Bode, J.W. Nat. Chem. 2014, 6,310. doi: 10.1038/nchem.1878 pmid: 24651197
	(c) Yanai, H. In Green Synthetic Approaches for Biologically Relevant Heterocycles, Ed.: Brahmachari, G., Elsevier, Boston, 2015, pp.257~289. pmid: 24651197
	(d) Meyer, A.G.; Bissember, A.C.; Hyland, C.J. T.; Williams, C.C.; Szabo, M.; Abel, S.A. G.; Bird, M.J.; Hyland, I.K.; Pham, H. In Progress in Heterocyclic Chemistry, Eds.: Gribble, G. W.; Joule, J.A., Elsevier, Amsterdam, 2018, pp.493~550. pmid: 24651197
[2]	(a) Yudin, A.K. Aziridines and Epoxides in Organic Synthesis, Wiley-VCH, Weinheim, 2006. pmid: 23488989
	(b) Kannan, V.; Sreekumar, K.; Gil, A.; Vicente, M.A. Catal. Lett. 2011, 141,1118. pmid: 23488989
	(c) Lykke, L.; Halskov, K.S.; Carlsen, B.D.; Chen, V.X.; Jørgensen, K.A. J. Am. Chem. Soc. 2013, 135,4692. doi: 10.1021/ja401150m pmid: 23488989
[3]	For selected reviews, see: (a) Aho, J. E.; Pihko, P. M.; Rissa, T. K. Chem. Rev. 2005, 105,4406. pmid: 31322898
	(b) Carey, F.A. Organic Chemistry, 6th ed., McGraw-Hill, New York, 2006. pmid: 31322898
	(c) Sawant, P.; Maier, M.E. Eur. J. Org. Chem., 2012,6576. pmid: 31322898
	(d) Čorić, I.; Vellalath, S.; Müller, S.; Cheng, X.; List, B. Top. Organomet. Chem. 2013, 44,165. pmid: 31322898
	(e) Kim, J.H.; Čorić, I.; Vellalath, S.; List, B. Angew. Chem., Int. Ed. 2013, 52,4474. pmid: 31322898
	(f) Nallasivam, J.L.; Fernandes, R.A. Org. Biomol. Chem. 2017, 15,708. pmid: 31322898
	(g) Yu, X.; Che, Z.; Xu, H. Chem.-Eur. J. 2017, 23,4467. doi: 10.1002/chem.201602472 pmid: 31322898
	(h) Mahto, P.; Rana, N.K.; Shukla, K.; Das, B.G.; Joshi, H.; Singh, V.K. Org. Lett. 2019, 21,5962. doi: 10.1021/acs.orglett.9b02094 pmid: 31322898
[4]	For selected reviews, see: (a) Bégué, J.-P.; Bonnet-Delpon, D.; Crousse, B.; Legros, J. Chem. Soc. Rev. 2005, 34,562. pmid: 24299176
	(b) Purser, S.; Moore, P.R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37,320. doi: 10.1039/b610213c pmid: 24299176
	(c) Xie, H.X.; Zhang, Y.; Zhan, S.L.; Cheng, X.B.; Wang, W. Angew. Chem., Int. Ed. 2011, 50,11773. pmid: 24299176
	(d) Ma, J.-A.; Cahard, D. Chem. Rev. 2008, 108,PR1. doi: 10.1021/cr800221v pmid: 24299176
	(e) Zheng, Y.; Ma, J.-A. Adv. Synth. Catal. 2010, 352,2745. pmid: 24299176
	(f) Nie, J.; Guo, H.-C.; Cahard, D.; Ma, J.-A. Chem. Rev. 2011, 111,455. pmid: 24299176
	(g) Kawai, H.; Tachi, K.; Tokunaga, E.; Shiro, M.; Shibata, N. Org. Lett. 2010, 12,5104. doi: 10.1021/ol102189c pmid: 24299176
	(h) Wang, T.; Zhang, G.-W.; Teng, Y.; Nie, J.; Zheng, Y.; Ma, J.-A. Adv. Synth. Catal. 2010, 352,2773. pmid: 24299176
	(i) Zhang, G.-W.; Meng, W.; Ma, H.; Nie, J.; Zhang, W.-Q.; Ma, J.-A. Angew. Chem., Int. Ed. 2011, 50,3538. pmid: 24299176
	(j) Allen, A.E.; MacMillan, D.W. C. J. Am. Chem. Soc. 2010, 132,4986. pmid: 24299176
	(k) Kawai, H.; Kitayama, T.; Tokunaga, E.; Shibata, N. Eur. J. Org. Chem. 2011, 30,5959. pmid: 24299176
	(l) Ma, H.; Matsuzaki, K.; Yang, Y.-D.; Tokunaga, E.; Nakane, D.; Ozawa, T.; Masuda, H.; Shibata, N. Chem. Commun. 2013, 49,11206. pmid: 24299176
	(m) Wang, J.; Sanchez-Rosello, M.; Aceña, J.L.; Pozo, C.; Sorochinsky, A.E.; Fustero, S.; Soloshonok, V.A.; Liu, H. Chem. Rev. 2014, 114,2432. doi: 10.1021/cr4002879 pmid: 24299176
[5]	(a) Wang, J.; Kong, W.-G.; Li, F.; Liu, J.; Shen, Q.; Liu, L.; Zhao, W.-X. Org. Biomol. Chem. 2015, 13,5399. pmid: 27390924
	(b) Lin, Y.-J.; Du, L.-N.; Kang, T.-R.; Liu, Q.-Z.; Chen, Z.-Q.; He, L. Chem.-Eur. J. 2015, 21,11773. doi: 10.1002/chem.201501897 pmid: 27390924
	(c) Zhu, Y.; Dong, Z.; Cheng, X.; Zhong, X.; Liu, X.; Lin, L.; Shen, Z.; Yang, P.; Li, Y.; Wang, H.; Yan, W.; Wang, R. Org. Lett. 2016, 18,3546. pmid: 27390924
[6]	(a) Li, F.; Wang, J.-J.; Xu, M.-M.; Zhao, X.-B.; Zhou, X.-H.; Zhao, W.-X.; Liu, L.-T. Org. Biomol. Chem. 2016, 14,3981. doi: 10.1039/c6ob00281a pmid: 27897299
	(b) Liliana, B.-F.; Elodie, B.; Michael, M.; Louis, J.F.; Claire, W.; Joëlle, P.; Diego, G.-S. Org. Biomol. Chem. 2017, 15,301. pmid: 27897299
[7]	For reviews on oxy-Michael addition reactions,see: (a) Nising, C. F.; Brase, S. Chem. Soc. Rev. 2008, 37,1218. pmid: 21796323
	(b) Hartmann, E.; Vyas, D.J.; Oestreich, M. Chem. Commun. 2011, 47,7917. pmid: 21796323
	(c) Nising, C.F.; Brase, S. Chem. Soc. Rev. 2012, 41,988. doi: 10.1039/c1cs15167c pmid: 21796323
[8]	(a) Li, D.R.; Murugan, A.; Falck, J.R. J. Am. Chem. Soc. 2008, 130,46. pmid: 18076175
	(b) Wang, H.F.; Yan, L.J.; Wu, Y.; Chen, F. Tetrahedron 2017, 73,2793. pmid: 18076175
[9]	(a) Asano, K.; Matsubara, S. Org. Lett. 2012, 14,1620. doi: 10.1021/ol3003755 pmid: 25384209
	(b) Okamura, T.; Asano, K.; Matsubara, S. Chem. Commun. 2012, 48,5076. pmid: 25384209
	(c) Fukata, Y.; Miyaji, R.; Okamura, T.; Asano, K.; Matsubara, S. Synthesis 2013, 45,1627. pmid: 25384209
	(d) Yoneda, N.; Hotta, A.; Asano, K.; Matsubara, S. Org. Lett. 2014, 16,6264. pmid: 25384209
[10]	(a) Fukata, Y.; Asano, K.; Matsubara, S. Chem. Lett. 2013, 42,355. pmid: 23844669
	(b) Asano, K.; Matsubara, S. J. Am. Chem. Soc. 2011, 133,16711. pmid: 23844669
	(c) Miyaji, R.; Asano, K.; Matsubara, S. Org. Lett. 2013, 15,3658. doi: 10.1021/ol401538b pmid: 23844669
[11]	(a) Reddy, B.V.; Reddy, S.M.; Swain, M. RSC Adv. 2013, 3,930.
	(b) Reddy, B.V.; Reddy, S.M.; Swain, M.; Dudem, S.; Kalivendib, S.V.; Reddy, C.S. RSC Adv. 2014, 4,9107.

三乙胺催化的γ-羟基-α,β-不饱和酮与三氟甲基酮通过半缩酮中间体的级联反应

Triethylamine-Catalyzed Cascade Reaction of γ-Hydroxy-α,β-unsaturated Ketones with Trifluoromethyl Ketones via Hemiketal Intermediates

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