N-Heterocyclic Carbene Catalyzed Esterification of Dicarbaldehydes with Arylboronic Acid for Axially Chiral Phosphorus Compounds

doi:10.6023/cjoc202504014

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (10): 3847-3855.DOI: 10.6023/cjoc202504014 Previous Articles Next Articles

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氮杂环卡宾催化双醛与芳基硼酸的酯化反应合成轴手性磷化合物

黄雪辉^a^,^b, 林艳如^a^,^b, 李兆迪^b, 张悦^b, 王鑫^b, 高媛媛^b, 宫晓杰^a, 李飞^a^,^*(), 刘澜涛^b^,^*()

^a 辽宁石油化工大学石油化工学院辽宁抚顺 113001
^b 商丘师范学院化学化工学院河南省药物绿色合成工程研究中心河南商丘 476000

收稿日期:2025-04-13 修回日期:2025-05-13 发布日期:2025-06-06
基金资助:
河南省自然科学基金(232300421234); 河南省自然科学基金(252300421726); 商丘市科技创新领军人才(SQRC202212004); 商丘师范学院黄河故道区生态环境保护计划资助项目

N-Heterocyclic Carbene Catalyzed Esterification of Dicarbaldehydes with Arylboronic Acid for Axially Chiral Phosphorus Compounds

Xuehui Huang^a^,^b, Yanru Lin^a^,^b, Zhaodi Li^b, Yue Zhang^b, Xin Wang^b, Gao Yuanyuan^b, Xiaojie Gong^a, Fei Li^a^,^*(), Lantao Liu^b^,^*()

^a School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun, Liaoning 113001
^b Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, Henan 476000

Received:2025-04-13 Revised:2025-05-13 Published:2025-06-06
Contact: * lnpulf@126.com; liult05@iccas.ac.cn.
Supported by:
Natural Science Foundation of Henan Province(232300421234); Natural Science Foundation of Henan Province(252300421726); Leading Talents in Scientific and Technological Innovation in Shangqiu(SQRC202212004); Program of Ecological Environmental Protection in the Area of Old Course of Yellow River of Shangqiu Normal University

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Abstract

Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging. Herein, an N-heterocyclic carbene (NHC) catalyzed esterification reaction of dialdehydes with arylboronic acids was developed, successfully constructing the framework of axially chiral phosphorus compounds. Mechanistic studies have revealed that the reaction initially undergoes a desymmetrization process, followed by a kinetic resolution pathway, affording a series of axially chiral phosphorus compounds with high enantioselectivity (up to 92% ee).

Key words: axially chiral phosphorus compounds, N-heterocyclic carbene, esterification, desymmetrization

Cite this article

Xuehui Huang, Yanru Lin, Zhaodi Li, Yue Zhang, Xin Wang, Gao Yuanyuan, Xiaojie Gong, Fei Li, Lantao Liu. N-Heterocyclic Carbene Catalyzed Esterification of Dicarbaldehydes with Arylboronic Acid for Axially Chiral Phosphorus Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3847-3855.

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氮杂环卡宾催化双醛与芳基硼酸的酯化反应合成轴手性磷化合物

N-Heterocyclic Carbene Catalyzed Esterification of Dicarbaldehydes with Arylboronic Acid for Axially Chiral Phosphorus Compounds

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Entry	preNHC	n(1)∶n(2a)	T/°C	Solvent	Time/h	Yield^b/% of 3a	ee^c/% of 3a	Yield^b/% of 4a
1	A	1∶1	60	Toluene	9	6	86	Trace
2	B	1∶1	60	Toluene	9	N.D.	—	—
3	C	1∶1	60	Toluene	9	15	92	14
4	D	1∶1	60	Toluene	9	13	67	5
5	E	1∶1	60	Toluene	9	12	85	6
6	C	1∶1	45	Toluene	9	24	91	17
7	C	1∶1	30	Toluene	17	21	57	13
8	C	1∶0.8	45	Toluene	7	41	43	27
9	C	1∶1.5	45	Toluene	6	26	92	19
10	C	1∶1.5	45	THF	6	21	46	27
11	C	1∶1.5	45	DCM	6	14	61	23
12^d	C	1∶1.5	45	Toluene	8	23	91	19
13^e	C	1∶1.5	45	Toluene	10	21	87	20