桥联碳硼烷膦化合物的合成及其在大位阻Suzuki偶联反应中的应用

doi:10.6023/cjoc202601020

摘要/Abstract

研究了桥联碳硼烷-二苯基膦化合物的合成、结构、稳定性及其在金属催化偶联反应中的初步应用. 邻碳硼烷锂盐与2-(二苯基膦基)苯甲醛反应, 生成二苯基膦基碳硼烷甲醇(1)和双(二苯基膦基)碳硼烷二甲醇(2). 化合物1发生羟基氯代反应生成1-(2'-二苯基膦基苯基)氯甲基邻碳硼烷(3), 而在空气中发生缓慢氧化则生成相应的膦氧化合物4. 化合物1和2的氧化稳定性较低, 在空气中发生缓慢氧化, 而氯代化合物3在相同条件下的氧化稳定性明显提高. 化合物1在碱性条件下很快分解为邻碳硼烷和2-(二苯基膦)苯甲醛, 在相同条件下氯代产物3则缓慢分解. 通过谱学方法或元素分析、单晶X射线衍射(1和2)和密度泛函理论(DFT)方法(1~3)研究了产物的组成和结构. 化合物3在钯催化的大位阻Suzuki偶联反应中展示了一定的潜力, 该结果为桥联碳硼烷膦化合物用于有机功能分子的催化合成提供了新的可能.

关键词: 碳硼烷, 膦化合物, 合成, 稳定性, Suzuki偶联

The synthesis, structures, stabilities of bridged carboranyl-diphenylphosphine compounds and their preliminary applications in metal-catalyzed coupling reactions are studied. The lithium salt of o-carborane reacts with 2-(diphenylphos-phino)benzaldehyde to produce bridged diphenylphosphinocarboranylmethanol (1) and bis(diphenylphosphino)-o-carboranyl-bismethanol (2). The chlorination of compound 1 produces 1-(2'-diphenylphosphinophenyl)chloromethyl-o-carborane (3), and compound 1 undergoes slow oxidation in air to produce corresponding phosphine oxide compound 4. The oxidation stabilities of 1 and 2 are relatively low, while the oxidation stability of the chlorinated compound 3 is significantly higher under the same conditions. Compound 1 readily decomposes into 2-(diphenylphosphine)benzaldehyde and o-carborane under basic conditions, whereas the chlorinated product 3 slowly decomposes under the same conditions. The structures of the products were studied by spectroscopic methods or elemental analysis, single crystal X-ray diffraction (1, 2) and density functional theory methods(1~3). Compound 3 exhibits potential in palladium catalyzed sterically demanding Suzuki coupling reactions, providing new possibilities for bridged o-carboranylphosphine compounds in the catalytic synthesis of organic functional molecules.

Key words: carborane, phosphine compound, synthesis, stability, Suzuki coupling

引用此文

张国英, 张雪玥, 苗金玲, 刘广宁, 王斌, 聂永. 桥联碳硼烷膦化合物的合成及其在大位阻Suzuki偶联反应中的应用[J]. 有机化学, 2026, 46(10): 4162-4171.

Guoying Zhang, Xueyue Zhang, Jinling Miao, Guangning Liu, Bin Wang, Yong Nie. Synthesis of Bridged o-Carboranylphosphine Compounds and Their Application in Sterically Demanding Suzuki Coupling Reaction[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4162-4171.

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图/表 11

图1. (a)已知的桥联、(b)混合型的邻碳硼烷膦化合物以及(c)本文研究的桥联邻碳硼烷膦化合物(未标注的顶点均为BH)

Figure 1. (a) Known bridged, (b) mixed type o-carboranyl-phosphine compounds, and (c) bridged o-carboranylphosphine compounds studied in this work (unlabeled vertices are BH)

Entry	o-C₂B₁₀H₁₂/equiv.	Base (Dosage/equiv.)	Aldehyde/equiv	Yield^a/% of 1	Yield^a/% of 2
1^b	1.0	n-BuLi (1.1)	1.0	39	25
2^c	1.0	KHMDS (1.1)	1.0	33	31
3^d	1.0	n-BuLi (1.1)	1.1	80	9
4	0.5	TBAF (3.8)	1.2	41	0
5^d	1.0	n-BuLi (2.1)	1.0	31	32
6^d	1.0	n-BuLi (2.1)	2.2	14	61

表1. 桥联碳硼烷膦化合物1和2的合成

Table 1. Synthesis of bridged o-carboranylphosphine compounds 1 and 2

图2. 化合物1的单晶结构(氢原子未画出, 椭球概率为30%)

Figure 2. Crystal structure of compound 1 (hydrogen atoms are omitted for clarity, ellipsoids are drawn at 30% probability)

图3. 化合物1晶体中分子内和分子间的相互作用(绿色虚线处的数值为原子间距或原子至环重心距离, nm)

Figure 3. Intramolecular and intermolecular interactions of compound 1 in crystals (the values near green dashed lines are interatomic or atom-centroid distances, nm)

图4. 化合物2的单晶结构(氢原子未画出, 删除了无序的溶剂水分子, 椭球概率为30%)

Figure 4. Crystal structure of compound 2 (hydrogen atoms and disordered water molecules are omitted for clarity, ellipsoids are drawn at 30% probability)

图5. 化合物2晶体中分子间的相互作用(绿色虚线处数值为原子间距或原子至环重心距离, nm)

Figure 5. Intermolecular and intramolecular interactions of compound 2 in crystals (the values near green dashed lines are interatomic or atom-centroid distances, nm)

图6. 化合物1的前线轨道及其能级

Figure 6. Frontier molecular orbitals and their energy levels of compound 1

图7. 化合物2的前线轨道及其能级

Figure 7. Frontier molecular orbitals and their energy levels of compound 2

图8. 化合物3的前线轨道及其能级

Figure 8. Frontier molecular orbitals and their energy levels of compound 3

图式1. 化合物1在空气中发生氧化以及在碱性条件下分解

Scheme 1. Oxidation in air and decomposition under basic condition of compound 1

Entry	Pd source	Ligand	Time/h	Yield^a/%
1	PdCl₂	None	32	32
2	PdCl₂	3	32	35
3^b	Pd₂(dba)₃	BI-DIME	24	87
4	Pd₂(dba)₃	3	25	80

表2. 化合物3在大位阻Suzuki偶联反应中的应用

Table 2. Application of compound 3 in sterically demanding Suzuki coupling reaction

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