Synthesis of Bridged o-Carboranylphosphine Compounds and Their Application in Sterically Demanding Suzuki Coupling Reaction

doi:10.6023/cjoc202601020

Abstract

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

Cite this article

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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Fig. & Tab. 11

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

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

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

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

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

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

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

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

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

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

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

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