Visible-Light-Induced Palladium-Catalyzed Cross-Coupling of Iodocarboranes with (Hetero)Arenes DOI
Shimeng Li, Jie Zhang, Zuowei Xie

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7497 - 7501

Published: Oct. 6, 2022

This work describes a general method for the efficient production of class cage B-centered carboranyl radicals at B3, B4, and B9 sites via visible-light-promoted palladium(0)/palladium(I) pathway using readily available iodo-o-carboranes as starting materials. The electrophilicities these hypervalent boron-centered decrease in following order: B3 > B4 B9. They are useful intermediates preparation family B-(hetero)arylated o-carboranes ambient temperature.

Language: Английский

Taming Inert B–H Bond with Low Energy Light: A Near-Infrared Light-Induced Approach to Facile Carborane Cluster-Amino Acid Coupling DOI

Sheng‐Wen Xu,

Hongjian Zhang,

Jibo Zong

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

The selective functionalization of inert B–H bonds in carborane clusters has been a formidable challenge. Recent advances have witnessed such reactions through photoredox methods utilizing ultraviolet or visible light irradiation. However, high-energy sources often suffer from poor energy efficiency, limited substrate scope, undesired side reactions, and low scalability. Here, we present the first successful bond under low-energy near-infrared (NIR) using carborane-based electron donor–acceptor complex. Both photophysical investigations theoretical modeling reveal facile single-electron transfer cage to electron-deficient photocatalyst, generating radical NIR follow-up pathway enables direct coupling carboranes with amino acids oligopeptides, yielding diverse array carborane-functionalized oligopeptides. Beyond expanding known chemical space boron cluster derivatives, further demonstrate that imaging targeting capabilities could serve as promising multifunctional carriers for neutron capture therapy. Thus, via not only provides straightforward practical strategy synthetic chemistry but also lays foundation development next-generation boron-containing biomolecules advanced functional materials.

Language: Английский

Citations

0
Post-coordination of Ru(II) Controlled Regioselective B(4)–H Acylmethylation of o-Carboranes with Sulfoxonium Ylides DOI Creative Commons
Hou‐Ji Cao, Jiaxin Li,

Jia-Hui Yan

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Despite significant progress in the B-H functionalization of carboranes, development cost-effective catalytic systems devoid noble metals, coupled with mechanistic validation regioselectivity control, remains a formidable challenge. Herein, we disclose an Ag salt-free, redox-neutral, and inexpensive ruthenium(ii)-catalyzed protocol that enables exclusive B(4)-H acylmethylation o-carboranes through novel post-coordination strategy. By exploiting weakly coordinating carboxylic acid as traceless directing group, this method achieves excellent mono-site selectivity for B-C(sp3) bond formation using diverse sulfoxonium ylides, demonstrating both functional group tolerance synthetic scalability. This work not only establishes practical platform but also addresses critical questions unresolved prior analogous studies. Through deuterium labeling, situ high-resolution mass spectrometry (HRMS) tracking, single-crystal X-ray analysis Ru intermediates, unequivocally demonstrate originates from unique mode Ru(ii). The catalyst simultaneously engages enolizable acylmethyl moiety mono-acylated intermediate, thereby dictating activation trajectory. Our findings establish generalizable regiocontrolled carborane while defining paradigms transition metal-mediated chemistry.

Language: Английский

Citations

0
The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals DOI
Wenjing Guo, Yang Zhao, Longlong Shu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 15, 2024

Carborane compounds, known for their exceptional thermal stability and non-toxic attributes, have garnered widespread utility in medicine, supramolecular design, coordination/organometallic chemistry, others. Although there is considerable interest among chemists, the integration of suitable carborane molecules into ferroelectric materials remains a formidable challenge. In this study, we employ quasi-spherical design strategy to introduce functional groups at boron vertices o-carborane cage, aiming reduce molecular symmetry. This approach led successful synthesis pioneering crystals composed cage-like carboranes: 9-OH-o-carborane (1) 9-SH-o-carborane (2), which undergo above-room phase transitions (T

Language: Английский

Citations

3
Highly selective electrophilic B(9)-amination of o-carborane driven by HOTf and HFIP DOI
Yan Wang, Hao Yan, Wenjing Guo

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 4975 - 4980

Published: Jan. 1, 2022

An efficient B(9) electrophilic amination of o -carboranes with azodicarboxylates, promoted by a Brønsted acid and HFIP, was developed.

Language: Английский

Citations

16
A Method for Highly Selective Halogenation of o-Carboranes and m-Carboranes DOI
Wen Lu,

Yanxuan Wu,

Yan‐Na Ma

et al.

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 62(2), P. 885 - 892

Published: Dec. 30, 2022

A facile halogenation method for highly selective synthesis of 9-X-o-carboranes, 9,12-X2-o-carboranes, 9-X-12-X'-o-carboranes, 9-X-m-carboranes, 9,10-X2-m-carboranes, and 9-X-10-X'-m-carboranes (X, X' = Cl, Br, I) has been developed on the basis our previous work. The success this transformation relies usage trifluoromethanesulfonic acid (HOTf), easily available strong Brønsted acid. addition HOTf greatly increases electrophilicity N-haloamides through hydrogen bonding interaction, resulting in low loading N-haloamides, short reaction time, mild conditions. Additionally, solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is also essential to further increase acidity HOTf.

Language: Английский

Citations

15
Visible-Light-Induced Iron Group Metal Catalysis: Recent Developments in Organic Synthesis DOI

Changzhen Yin,

Miao Wang,

Zhenxi Cai

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(22), P. 4864 - 4882

Published: Aug. 8, 2022

Abstract One central research goal for modern organic chemistry in society is to develop sustainable synthetic methodologies. Visible-light-induced transformations that apply earth-abundant metals as catalysts are a good reply this concern. In short review, recent developments of photocatalysis applying iron group metal (Fe, Co, Ni) discussed. Reaction types, the catalyst details, and mechanisms introduced. 1 Introduction 2 Visible-Light-Induced Fe-Catalyzed Reactions 3 Co-Catalyzed 4 Ni-Catalyzed 5 Summary

Language: Английский

Citations

13
Iridium-Catalyzed Selective B(4)–H Amination of o-Carboranes with Anthranils DOI
Lin‐Bao Zhang, Zuowei Xie

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7077 - 7081

Published: Sept. 23, 2022

We report here a catalytic selective cage B4-H amination of o-carboranes employing an Ir(III) complex as catalyst and anthranils aminating agents, leading to large class B4-aminated with very high yields broad substrate scope under mild conditions without any oxidants. In these reactions, the carboxyl group serves traceless directing unit determine site selectivity degree substitution.

Language: Английский

Citations

13
Visible‐Light‐Promoted Palladium‐Catalyzed Cross‐Coupling of Iodocarboranes with Disulfides and Phenylselenyl Chloride† DOI Open Access
Shimeng Li, Yizhen Liu, Zuowei Xie

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(2), P. 129 - 134

Published: Sept. 19, 2023

Comprehensive Summary This work describes a general method for the synthesis of series sulfenylated and selenylated carboranes at room temperature using readily available iodocarboranes as starting materials via boron‐centered carboranyl radicals. Such hypervalent boron radicals are generated by visible‐light‐promoted Pd(0)/Pd(I) pathway. They useful intermediates can be trapped disulfides phenylselenyl chloride convenient construction B—S/Se bonds.

Language: Английский

Citations

7
Iron-Catalyzed Selective B–H Activation for 4/5-fold Methylation and Arylation of Carboranes DOI
Peng Zhou, Yu Chen, Zuowei Xie

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 8761 - 8767

Published: July 7, 2022

Catalytic selective B–H functionalization of carboranes has recently attracted enormous research interest, resulting in the development a series methods for transition metal-catalyzed vertex-specific carboranes. These established protocols require noble metal catalysts. Herein, we report highly efficient iron-catalyzed silver-free 4/5-fold cage methylation/arylation using organoaluminum compounds as alkylation/arylation reagents, leading to variety B(3,4,5,6)-tetramethylated/tetraarylated o-carboranes and B(2,3,4,5,6)-pentamethylated/pentaphenylated m-carboranes very good excellent yields. The use inexpensive diethyl oxalate an oxidant makes this protocol practical, realizing easily gram-scale synthesis products. associated reaction mechanism is also proposed. This method represents alternative strategy catalytic polyfunctionalization via base catalysis.

Language: Английский

Citations

12
Formation and reactivity of a unique M⋯C–H interaction stabilized by carborane cages DOI Creative Commons

Xin-Ran Liu,

Peng‐Fei Cui, Yago García‐Rodeja

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9274 - 9280

Published: Jan. 1, 2024

Broadening carborane applications has consistently been the goal of chemists in this field. Herein, compared to alkyl or aryl groups, a cage demonstrates an advantage stabilizing unique bonding interaction: M⋯C–H interaction.

Language: Английский

Citations

2