甲醇为氢源的α-芳基亚胺酸酯不对称转移氢化反应

doi:10.6023/cjoc202204047

有机化学 ›› 2022, Vol. 42 ›› Issue (11): 3693-3703.DOI: 10.6023/cjoc202204047 上一篇下一篇

研究论文

甲醇为氢源的α-芳基亚胺酸酯不对称转移氢化反应

王婷^a, 陈景超^a^,^*(), 王轮^a, 王喆婷^a, 樊保敏^a^,^b^,^*()

^a云南民族大学民族药资源化学国家民委-教育部重点实验室昆明 650500
^b云南民族大学化学与环境学院昆明 650500

收稿日期:2022-04-18 修回日期:2022-07-11 发布日期:2022-08-10
通讯作者: 陈景超, 樊保敏
基金资助:
国家自然科学基金(21961045); 国家自然科学基金(22061048)

Asymmetric Transfer Hydrogenation of α-Aryl Amidates Using Methanol as Hydrogen Source

Ting Wang^a, Jingchao Chen^a(), Lun Wang^a, Zheting Wang^a, Baomin Fan^a^,^b()

^aKey Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & Ministry of Education, Yunnan Minzu University, Kunming 650500
^bSchool of Chemistry and Environment, Yunnan Minzu University, Kunming 650500

Received:2022-04-18 Revised:2022-07-11 Published:2022-08-10
Contact: Jingchao Chen, Baomin Fan
Supported by:
National Natural Science Foundation of China(21961045); National Natural Science Foundation of China(22061048)

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摘要/Abstract

手性芳基甘氨酸作为氨基酸衍生物的一种, 不仅在有机合成领域中具有非常重要的应用价值, 还是许多手性药物和生物活性化合物的关键结构单元. 报道了一种实用、经济的制备手性α-芳基甘氨酸的方法. 以甲醇为氢源, 在Pd/ Zn共催化体系下, α-芳基亚胺酸酯发生不对称转移加氢反应, 获得了一系列手性α-芳基甘氨酸衍生物, 同时以氘代甲醇为氘源获得了一系列手性氘代α-芳基甘氨酸衍生物. 该催化体系具有良好的底物适用性, 收率高达93%, 对映选择性高达92%, 氘代率高达94%, 为获得有价值的氘标记手性氨基酸提供了一种高效、经济的手段.

关键词: 甲醇, 亚胺酸脂, 氘代氨基酸, 不对称转移氢化

As a kind of amino acid derivatives, chiral arylglycine not only has very important application value in the field of organic synthesis, but also serves as the key structure of many chiral drugs and biologically active compounds. A practical and economical method for the preparation of chiral α-arylglycines is reported herein. By using methanol as the hydrogen source, a series of chiral α-arylglycine derivatives were prepared by asymmetric transfer hydrogenation of α-aryl imine esters with Pd/Zn co-catalyzed system. By switching the hydrogen source to deuterated methanol, a series of chiral deuterated a-arylglycine derivatives were obtained. The catalytic system featured with good substrate suitability, and the product was obtained in up to 93% yield with up to 92% enantioselectivity, and the deuteration incorporation rate is up to 94%. The present method has provided an efficient and economic method for the synthesis of valuable deuterium-labeled chiral amino acids.

Key words: methanol, imino acid, deuterium amino acid, asymmetric transfer hydrogenation

引用此文

王婷, 陈景超, 王轮, 王喆婷, 樊保敏. 甲醇为氢源的α-芳基亚胺酸酯不对称转移氢化反应[J]. 有机化学, 2022, 42(11): 3693-3703.

Ting Wang, Jingchao Chen, Lun Wang, Zheting Wang, Baomin Fan. Asymmetric Transfer Hydrogenation of α-Aryl Amidates Using Methanol as Hydrogen Source[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3693-3703.

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Entry^a	Ligand	Additive	Solvent	Time/h	Yield^b/%	ee^c/%
1	(R)-BINAP	Zn(OTf)₂	DCE	25	77	70
2	(R)-SEGPHOS	Zn(OTf)₂	DCE	12	81	84
3	(R)-P-PHOS	Zn(OTf)₂	DCE	3	86	84
4	(R)-MeO-BIPHEP	Zn(OTf)₂	DCE	40	46	80
5	(R)-SYNPHOS	Zn(OTf)₂	DCE	40	40	75
6	(R)-DM-SEGPHOS	Zn(OTf)₂	DCE	58	85	55
7	(S)-DTB-Meo-BIPHEP	Zn(OTf)₂	DCE	60	21	23
8	(R)-P-PHOS	Cu(OTf)₂	DCE	48	43	84
9	(R)-P-PHOS	CuOTf	DCE	48	31	83
10	(R)-P-PHOS	AgOTf	DCE	48	55	83
11	(R)-P-PHOS	ZnBr₂	DCE	48	Trace	—
12	(R)-P-PHOS	TBAI	DCE	48	Trace	—
13	(R)-P-PHOS	TBFPB	DCE	48	Trace	—
14	(R)-P-PHOS	Zn(OTf)₂	1,4-Dioxane	48	Trace	—
15	(R)-P-PHOS	Zn(OTf)₂	THF	48	Trace	—
16	(R)-P-PHOS	Zn(OTf)₂	DMF	48	Trace	—
17	(R)-P-PHOS	Zn(OTf)₂	MeCN	48	Trace	—
18	(R)-P-PHOS	Zn(OTf)₂	Toluene	48	Trace	—
19^d	(R)-P-PHOS	Zn(OTf)₂	DCE	3	85	84
20^e	(R)-P-PHOS	Zn(OTf)₂	DCE	24	60	84
21^f	(R)-P-PHOS	Zn(OTf)₂	DCE	5	86	84
22^g	(R)-P-PHOS	Zn(OTf)₂	DCE	7	84	84

Entry^a	Ligand	Additive	Solvent	Time/h	Yield^b/%	ee^c/%
1	(R)-BINAP	Zn(OTf)₂	DCE	25	77	70
2	(R)-SEGPHOS	Zn(OTf)₂	DCE	12	81	84
3	(R)-P-PHOS	Zn(OTf)₂	DCE	3	86	84
4	(R)-MeO-BIPHEP	Zn(OTf)₂	DCE	40	46	80
5	(R)-SYNPHOS	Zn(OTf)₂	DCE	40	40	75
6	(R)-DM-SEGPHOS	Zn(OTf)₂	DCE	58	85	55
7	(S)-DTB-Meo-BIPHEP	Zn(OTf)₂	DCE	60	21	23
8	(R)-P-PHOS	Cu(OTf)₂	DCE	48	43	84
9	(R)-P-PHOS	CuOTf	DCE	48	31	83
10	(R)-P-PHOS	AgOTf	DCE	48	55	83
11	(R)-P-PHOS	ZnBr₂	DCE	48	Trace	—
12	(R)-P-PHOS	TBAI	DCE	48	Trace	—
13	(R)-P-PHOS	TBFPB	DCE	48	Trace	—
14	(R)-P-PHOS	Zn(OTf)₂	1,4-Dioxane	48	Trace	—
15	(R)-P-PHOS	Zn(OTf)₂	THF	48	Trace	—
16	(R)-P-PHOS	Zn(OTf)₂	DMF	48	Trace	—
17	(R)-P-PHOS	Zn(OTf)₂	MeCN	48	Trace	—
18	(R)-P-PHOS	Zn(OTf)₂	Toluene	48	Trace	—
19^d	(R)-P-PHOS	Zn(OTf)₂	DCE	3	85	84
20^e	(R)-P-PHOS	Zn(OTf)₂	DCE	24	60	84
21^f	(R)-P-PHOS	Zn(OTf)₂	DCE	5	86	84
22^g	(R)-P-PHOS	Zn(OTf)₂	DCE	7	84	84

甲醇为氢源的α-芳基亚胺酸酯不对称转移氢化反应

Asymmetric Transfer Hydrogenation of α-Aryl Amidates Using Methanol as Hydrogen Source

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