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

doi:10.6023/cjoc202211019

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (8): 2946-2952.DOI: 10.6023/cjoc202211019 Previous Articles Next Articles

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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Abstract

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

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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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References 7

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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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References 7

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[1]	Suo Yongbo, Xie Mingsheng, Chen Yangguang, Zhang Yiming, Guo Zhen, Li Jianping, Qu Guirong, Guo Haiming. Synthesis of 1,2,3,4-Tetrazine Derivatives via [4+2] Cycloaddition of α-Halo-N-acylhydrazones with Diazodicarboxylates [J]. Chin. J. Org. Chem., 2016, 36(3): 540-546.
[2]	Xu Xiaoliang, Cheng Guohua, Li Xiaonian. Application of Azodicarboxylates in Organic Synthesis [J]. Chin. J. Org. Chem., 2012, 32(06): 1024-1040.