Pd(II)-catalyzed B(9)-alkynylation of o/m-carboranes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(23), С. 6706 - 6711

Опубликована: Янв. 1, 2024

Pd( ii )-catalyzed selective B(9)-alkynylation of o -carboranes and m with i Pr 3 SiCCBr as the alkynylated reagent was developed. Further transformation products provided diverse carborane derivatives.

Язык: Английский

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Palladium-Catalyzed Cross-Coupling Reactions of Carboranes with Alkenes via Selective B–H Bond Activation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

A palladium-catalyzed Heck-type cross-coupling reaction of carboranes with alkenes in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was realized. This shows good B(9) selectivity for m-carboranes and is also suitable o- p-carborane. Meanwhile, a series mono-, di-, trisubstituted were compatible substrates to afford the alkenylated products 16–89% yields. The 1,2-bis(carboranyl)ethylene first synthesized by vinyltrimethylsilane m-carborane. Further transformations C═C bond product examined hydroboration oxidation, hydroboration, bromination generate corresponding B(9)-functionalized m-carboranes.

Язык: Английский

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Polyoxometalate-Supported Pd(II)-Catalyzed B(9)–H Nitration of o/m-Carboranes

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 7646 - 7652

Опубликована: Апрель 23, 2025

Язык: Английский

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A comparative study on nido- and closo-carborane supported zinc-salen catalysts for the ROCOP of epoxides and anhydrides

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Nido -C 2 B 9 carborane anion supported Zn–salen complexes are superior to closo -carborane ones in ROCOP of epoxides and anhydrides.

Язык: Английский

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A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

The palladium-catalyzed generation of bis(o-carborane)s via regioselective B-B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential B4-H activation, B4'-H/B5'-H and reductive elimination, yielding ultimately. palladium catalyst tends to experience a Pd(II) → Pd(0) rather than Pd(IV) catalytic cycle, in which second B-H (B4'-H/B5'-H) activation serves as rate-determining step (RDS). Computed RDS step's barriers (27.0/29.0 kcal·mol-1, TS2a_I/TS2a'_I) consist well with experimental yields selectivities (P1a:P2a = 57%:23%). regioselectivity primarily controlled process, electronic effect playing key role steric hindrance influencing somewhat, confirmed natural bond orbital (NBO) noncovalent interaction (NCI) analyses. free-energy (27.0/29.6/31.1 kcal·mol-1) for AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted a_II), AgOAc-assisted a_III) cases agree perfectly corresponding trends (obtained 57%/43%/12% P1a, respectively). Theoretical predictions substituent effects also demonstrate consistency observations. This perfect agreement between experiments computations validates providing crucial insights into o-carboranes thus aiding controllable synthesis carborane materials.

Язык: Английский

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硼团簇及其材料化学研究进展(II): 硼碳团簇及化合物的相似性

Scientia Sinica Chimica, Год журнала: 2024, Номер unknown

Опубликована: Июль 8, 2024

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