ANIPE-Ligand-Enabled Copper-Catalyzed Asymmetric Carboboronation of Allenes with Imines and Diborons

doi:10.6023/cjoc202401027

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (6): 1884-1896.DOI: 10.6023/cjoc202401027 Previous Articles Next Articles

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ANIPE配体促进的铜催化联烯与亚胺和联硼试剂的不对称碳硼化反应

刘晓东, 施世良^*()

中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

收稿日期:2024-01-20 修回日期:2024-03-04 发布日期:2024-03-12
基金资助:
国家重点研发计划(2022YFA1503702); 国家重点研发计划(2021YFF0701600); 国家自然科学基金(22325110); 国家自然科学基金(92256303); 国家自然科学基金(21821002); 国家自然科学基金(22171280); 中国科学院战略性先导科技专项(XDB061000); 上海市优秀学术带头人计划(22XD1424900); 中国科学院青年交叉团队(JCTD-2021-11); 宁波市自然科学基金(2022J017)

ANIPE-Ligand-Enabled Copper-Catalyzed Asymmetric Carboboronation of Allenes with Imines and Diborons

Xiaodong Liu, Shiliang Shi^*()

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2024-01-20 Revised:2024-03-04 Published:2024-03-12
Contact: * E-mail: shiliangshi@sioc.ac.cn
Supported by:
National Key R&D Program of China(2022YFA1503702); National Key R&D Program of China(2021YFF0701600); National Natural Science Foundation of China(22325110); National Natural Science Foundation of China(92256303); National Natural Science Foundation of China(21821002); National Natural Science Foundation of China(22171280); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB061000); Program of Shanghai Academic Research Leader(22XD1424900); CAS Youth Interdisciplinary Team(JCTD-2021-11); Ningbo Natural Science Foundation(2022J017)

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Abstract

A diastereo- and enantioselective copper-catalyzed carboboronation of allene with aldimines and diborons under mild conditions is developed. This protocol is enabled by a chiral ANIPE-based copper catalyst, providing a facile and efficient approach to chiral homoallylic amines bearing two adjacent stereocenters with high enantioselectivities and diastereoselectivities. Besides, aldiminoester and ketiminoester could both serve as competent electrophiles for the production of enantioenriched α-amino esters.

Key words: N-heterocyclic carbene (NHC) ligand, copper catalysis, chiral amine, carboboronation

Cite this article

Xiaodong Liu, Shiliang Shi. ANIPE-Ligand-Enabled Copper-Catalyzed Asymmetric Carboboronation of Allenes with Imines and Diborons[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1884-1896.

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Fig. & Tab. 7

Figure 1. Selected bioactive molecules and ligands containing homoallylic amines

Scheme 1. Catalytic asymmetric carboboronation of allenes and dienes

Entry	Cat.	Solvent	Yield/%	dr	er^b
1	Cat. I	2-Me-THF	94	82:18	75.5:24.5
2	Cat. II	2-Me-THF	95	83:17	79.5:20.5
3	Cat. III	2-Me-THF	95	86:14	92:8
4	Cat. III	2-Me-THF	95	87:13	91.5:8.5
5	Cat. III	Toluene	63	86:14	88:12
6	Cat. III	MTBE	80	93:7	80:20
7^d	Cat. III	2-Me-THF	89 (82)^c	93:7	95.5:4.5
8^d^,^e	Cat. III	2-Me-THF	87	93:7	95:5

Table 1. Optimization of reaction conditionsa

Table 2. Substrate scope

Scheme 2. Synthesis of homoallylic amino esters Reaction conditions: amino ester (0.1 mmol), 2a (0.15 mmol), 3a (0.13 mmol), EtOH (0.2 mmol), catalyst (5 mol%) was stirred at r.t. for 24 h in 2-Me-THF (2.0 mL) under N2 atmosphere. Yield and diastereoselectivity were determined by 1H NMR analysis of the crude mixture. Determined by HPLC analysis. Isolated yield.

Scheme 3. Gram-scale reaction and transformation

Scheme 4. Proposed reaction mechanism

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ANIPE配体促进的铜催化联烯与亚胺和联硼试剂的不对称碳硼化反应

ANIPE-Ligand-Enabled Copper-Catalyzed Asymmetric Carboboronation of Allenes with Imines and Diborons

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