手性噁唑硼烷催化芳基磷氧对α,β-双功能不饱和化合物的不对称膦氢化反应研究

doi:10.6023/A24050166

化学学报 ›› 2024, Vol. 82 ›› Issue (7): 742-747.DOI: 10.6023/A24050166 上一篇下一篇

研究论文

手性噁唑硼烷催化芳基磷氧对α,β-双功能不饱和化合物的不对称膦氢化反应研究

高琦^a^,^b, 陈丽蓉^a^,^b, 钱金一^b, 樊瑞峰^b, 孙蔚青^a, 郭亚飞^a^,^*(), 樊保敏^a^,^*()

a 云南民族大学云南省手性物质研究与利用重点实验室昆明 650500
b 云南民族大学民族药资源化学教育部重点实验室昆明 650500

投稿日期:2024-05-22 发布日期:2024-06-12
基金资助:
国家自然科学基金(22361053); 国家自然科学基金(21961045); 云南省基础研究计划(202301AU070125); 云南省基础研究计划(202401BC070018); 云南省手性物质研究与利用重点实验室项目(202402AN360010); 云南省“兴滇英才”青年专项项目资助

Asymmetric Hydrophosphination of Diarylphosphine Oxides to α,β-Unsaturated Bifunctional Compounds Catalyzed by Chiral Oxazaborolidine

Qi Gao^a^,^b, Lirong Chen^a^,^b, Jinyi Qian^b, Ruifeng Fan^b, Weiqing Sun^a, Yafei Guo^a^,^*(), Baomin Fan^a^,^*()

a Yunnan Key Laboratory of Chiral Functional Substance Research and Application, Yunnan Minzu University, Kunming 650500, China
b Key Laboratory of Chemistry in Ethnic Medicinal Resources, Ministry of Education, Yunnan Minzu University, Kunming 650500, China

Received:2024-05-22 Published:2024-06-12
Contact: *E-mail: 041911@ymu.edu.cn;fanbaomin1979@163.com
Supported by:
National Natural Science Foundation of China(22361053); National Natural Science Foundation of China(21961045); Yunnan Fundamental Research Projects(202301AU070125); Yunnan Fundamental Research Projects(202401BC070018); Yunnan Key Laboratory of Chiral Functional Substance Research and Application(202402AN360010); “Yunnan Rejuvenation Talent”

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1. Supporting Information-A24050166.pdf(12973KB)

摘要/Abstract

手性噁唑硼烷催化剂(CBS)作为一种经典的非金属催化剂, 被广泛地用于酮的不对称还原和不对称环加成反应. 本工作报道了一种使用CBS催化剂, 实现二芳基磷氧亲核试剂对α,β-双功能不饱和化合物的不对称Michael加成反应. 该反应的可能催化机理与早期报道的CBS催化机理不同, CBS在此反应中很有可能是作为一个路易斯酸碱对, 通过裂解亲核试剂的氢氧键, 进而通过协同加成的过程, 实现不对称膦Michael加成反应. 另外, 该反应具有底物适用性良好、反应条件温和(室温)、对空气水分不敏感、易于放大等优点, 在合成手性膦配体领域具有潜在的应用价值.

关键词: 噁唑硼烷, 芳基磷氧, α,β-不饱和化合物, 不对称膦氢化

Oxazaborolidines (CBS) have been widely utilized as organocatalysts in enantioselective organic synthesis over the past thirty years, particularly for the asymmetric reduction of ketones and enantioselective cycloaddition reactions. The history of oxazaborolidines functioning as chiral Lewis acids has demonstrated that CBS requires activation by strong protonic acids or Lewis acids to enhance the Lewis acidity of boron, such as TfOH, Tf₂NH, and AlBr₃. In our previous work, we introduced a new application of CBS in the asymmetric 1,4-addition of diarylphosphine oxides to α,β-unsaturated ketones and esters. Unlike traditional CBS-catalyzed reactions, this catalytic system does not require strong protonic acids or Lewis acids to activate CBS; instead it likely functions as a Lewis pair to cleave the O—H bond and provide a chiral phosphorous intermediate. To further expand the application of this new method, we selected α,β-unsaturated bifunctional compounds bearing both a ketone and an amide group on either side of the double bond as substrates for this study. Initially, several oxazaborolidines and reaction conditions were explored for the model reaction. The results indicated that under optimal conditions (20 mol% Me-CBS at room temperature in acetonitrile for 2 h), the reaction proceeded well with high yield (99%) and high enantiomeric excess (93% ee). Subsequently, various substrates were examined under these optimal conditions yielding products with 52%~99% yields and 63%~99% ee. The general procedure involved stirring a mixture of substrates (0.24 mmol, 1.2 equiv.), diarylphosphine oxides (0.2 mmol, 1 equiv.), and CBS (20 mol% Me-CBS) in 2 mL acetonitrile for 2 h followed by purification via flash column chromatography. Finally, the potential mechanism behind how the catalyst functions as a Lewis pair to control enantioselectivity was discussed. Additionally, the chiral products have potential applications in synthesizing valuable phosphine ligands.

Key words: oxazaborolidine, diarylphosphine oxide, α,β-unsaturated compounds, asymmetric hydrophosphination

引用此文

高琦, 陈丽蓉, 钱金一, 樊瑞峰, 孙蔚青, 郭亚飞, 樊保敏. 手性噁唑硼烷催化芳基磷氧对α,β-双功能不饱和化合物的不对称膦氢化反应研究[J]. 化学学报, 2024, 82(7): 742-747.

Qi Gao, Lirong Chen, Jinyi Qian, Ruifeng Fan, Weiqing Sun, Yafei Guo, Baomin Fan. Asymmetric Hydrophosphination of Diarylphosphine Oxides to α,β-Unsaturated Bifunctional Compounds Catalyzed by Chiral Oxazaborolidine[J]. Acta Chimica Sinica, 2024, 82(7): 742-747.

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图/表 7

图1. (A) CBS催化的应用. (B) 课题组前期工作. (C) 4-氧代丁烯酰胺与二苯基磷氧的不对称Michael加成反应

Figure 1. (A) The applications of CBS. (B) Our previous work. (C) Asymmetric Michael addition reaction of 4-oxobutenamide with diaryl- phosphine oxides

Entry	Cat	Cat/mol%	Time/h	Yield^b/%	ee^c/%
1	Cat 1	20	2	99	93
2	Cat 2	20	2	87	22
3	Cat 3	20	2	92	73
4	Cat 4	20	2	76	1
5	Cat 1	5	2	90	63
6	Cat 1	10	2	95	90
7	Cat 1	15	2	96	90
8	Cat 1	30	2	90	93

表1. 催化剂种类和用量的筛选a

Table 1. Screening of catalyst type and dosagea

Entry	Solvent	Time/h	Yield^b/%	ee^c/%
1	ACN	2	99	93
2	Toluene	2	99	80
3	DCM	2	92	88
4	DCE	2	96	89
5	1,4-Dioxane	2	98	91
6	DMF	2	40	54

表2. 溶剂的筛选a

Table 2. Screening of solvents

Entry	T/℃	Time/h	Yield^b/%	ee^c/%
1	0	2	47	76
2	r.t.	2	99	93
3	40	2	96	92
4	60	2	97	93

表3. 温度的筛选a

Table 3. Screening of temperature

图2. 底物普适性的考察

Figure 2. Substrate scope of the reaction

图3. 手性膦化合物的转化

Figure 3. Transformation of chiral phosphine compounds

图4. 可能的反应机理

Figure 4. Possible reaction mechanism

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手性噁唑硼烷催化芳基磷氧对α,β-双功能不饱和化合物的不对称膦氢化反应研究

Asymmetric Hydrophosphination of Diarylphosphine Oxides to α,β-Unsaturated Bifunctional Compounds Catalyzed by Chiral Oxazaborolidine

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