银催化的β,γ-不饱和酰胺的不对称γ-胺化反应

doi:10.6023/cjoc202211019

有机化学 ›› 2023, Vol. 43 ›› Issue (8): 2946-2952.DOI: 10.6023/cjoc202211019 上一篇下一篇

研究论文

银催化的β,γ-不饱和酰胺的不对称γ-胺化反应

丁俊, 史啸坤, 郝宇, 白贺元^*(), 张书宇

上海交通大学化学化工学院上海 200240

收稿日期:2022-11-16 修回日期:2023-03-05 发布日期:2023-04-07
基金资助:
国家自然科学基金(22071147)

Silver-Catalyzed Enantioselective Intermolecular γ-Amination of β,γ-Unsaturated Amide

Jun Ding, Xiaokun Shi, Yu Hao, Heyuan Bai(), Shuyu Zhang

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Received:2022-11-16 Revised:2023-03-05 Published:2023-04-07
Contact: *E-mail: baiheyuan90@sjtu.edu.cn
Supported by:
The National Natural Science Foundation of China(22071147)

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摘要/Abstract

非天然的γ-氨基酸结构广泛存在于天然产物与药物分子中, 因此通过直接的不对称胺化反应合成非天然氨基酸衍生物具有重要的研究意义和应用价值. 以偶氮二甲酸酯为氮源, 一价银为催化剂, 联苯类轴手性双膦化合物为配体, 高效地实现了偶氮二甲酸酯与β,γ-不饱和酰胺的不对称反应. 该反应具有良好的底物适用性, 以中等的收率获得了一系列的手性γ-氨基酸衍生物, 产物对映选择性可以达到90%.

关键词: 不对称γ-胺化反应, 银催化反应, 偶氮二甲酸酯

Unnatural γ-amino acid structures are widely present in natural products and drug molecules. Therefore, the synthesis of unnatural amino acids through direct asymmetric amination reaction has important research and application values. An efficient γ-amination reaction using azodicarboxylate as nitrogen source is reported. The asymmetric reaction of azodicarboxylate with β,γ-unsaturated amides was realized by using monovalent silver as Lewis acid catalyst and biphenyl axial chiral bisphosphine compound as ligand. The reaction has good substrate applicability, and a series of chiral γ-amino acid derivatives were obtained in moderate yields with an enantioselectivity of 90% ee.

Key words: enantioselective γ-amination, silver-catalyzed reaction, azodicarboxylates

引用此文

丁俊, 史啸坤, 郝宇, 白贺元, 张书宇. 银催化的β,γ-不饱和酰胺的不对称γ-胺化反应[J]. 有机化学, 2023, 43(8): 2946-2952.

Jun Ding, Xiaokun Shi, Yu Hao, Heyuan Bai, Shuyu Zhang. Silver-Catalyzed Enantioselective Intermolecular γ-Amination of β,γ-Unsaturated Amide[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2946-2952.

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Entry	Ag	Ligand	Base	Solvent	Temp./℃	Yield^b/%	Ee^c/%
1	AgOAc	(R)-BINAP	DIPEA	THF	r.t.	50	51
2	AgBF₄	(R)-BINAP	DIPEA	THF	r.t.	42	62
3	AgPF₆	(R)-BINAP	DIPEA	THF	r.t.	39	53
4	AgOTf	(R)-BINAP	DIPEA	THF	r.t.	57	65
5	AgOTf	(R)-Tol-BINAP	DIPEA	THF	r.t.	56	59
6	AgOTf	(R)-DIOP	DIPEA	THF	r.t.	38	－21
7	AgOTf	(R)-MeO-TolBIPHEP	DIPEA	THF	r.t.	60	85
8	AgOTf	(R)-MeO-DTEMBIPHEP	DIPEA	THF	r.t.	51	63
9	AgOTf	(R)-SEGPHOS	DIPEA	THF	r.t.	36	68
10	AgOTf	(R)-DTEM-SEGPHOS	DIPEA	THF	r.t.	23	51
11	AgOTf	(R)-Ph-Garphos	DIPEA	THF	r.t.	64	81
12	AgOTf	(R)-Phosphine	DIPEA	THF	r.t.	42	-5
13	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	r.t.	73	87
14	AgOTf	(R)-MeO-BIPHEP	Et₃N	THF	r.t.	37	86
15	AgOTf	(R)-MeO-BIPHEP	DABCO	THF	r.t.	23	83
16	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	0	67	89
17	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	－10	51	87
18	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	－20	32	85

Entry	Ag	Ligand	Base	Solvent	Temp./℃	Yield^b/%	Ee^c/%
1	AgOAc	(R)-BINAP	DIPEA	THF	r.t.	50	51
2	AgBF₄	(R)-BINAP	DIPEA	THF	r.t.	42	62
3	AgPF₆	(R)-BINAP	DIPEA	THF	r.t.	39	53
4	AgOTf	(R)-BINAP	DIPEA	THF	r.t.	57	65
5	AgOTf	(R)-Tol-BINAP	DIPEA	THF	r.t.	56	59
6	AgOTf	(R)-DIOP	DIPEA	THF	r.t.	38	－21
7	AgOTf	(R)-MeO-TolBIPHEP	DIPEA	THF	r.t.	60	85
8	AgOTf	(R)-MeO-DTEMBIPHEP	DIPEA	THF	r.t.	51	63
9	AgOTf	(R)-SEGPHOS	DIPEA	THF	r.t.	36	68
10	AgOTf	(R)-DTEM-SEGPHOS	DIPEA	THF	r.t.	23	51
11	AgOTf	(R)-Ph-Garphos	DIPEA	THF	r.t.	64	81
12	AgOTf	(R)-Phosphine	DIPEA	THF	r.t.	42	-5
13	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	r.t.	73	87
14	AgOTf	(R)-MeO-BIPHEP	Et₃N	THF	r.t.	37	86
15	AgOTf	(R)-MeO-BIPHEP	DABCO	THF	r.t.	23	83
16	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	0	67	89
17	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	－10	51	87
18	AgOTf	(R)-MeO-BIPHEP	DIPEA	THF	－20	32	85

银催化的β,γ-不饱和酰胺的不对称γ-胺化反应

Silver-Catalyzed Enantioselective Intermolecular γ-Amination of β,γ-Unsaturated Amide

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