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

doi:10.6023/cjoc202204047

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (11): 3693-3703.DOI: 10.6023/cjoc202204047 Previous Articles Next Articles

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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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Abstract

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

Cite this article

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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Fig. & Tab. 7

References 19

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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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