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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(36)

Опубликована: Июнь 15, 2024

Abstract 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‐ ( 1 ) 9‐SH‐ 2 ), which undergo above‐room phase transitions T c approximately 367 K 347 K. Interestingly, represent uniaxial multiaxial ferroelectrics respectively, with exhibiting six polar axes as many twelve equivalent polarization directions. As instance crystals, study introduces novel structural archetype ferroelectrics, thereby providing fresh insights exploration promising applications.

Язык: Английский

Organocatalytic Asymmetric Synthesis of o-Carboranyl Amines DOI
Hong‐Lei Xu,

Minghui Zhu,

Herman H. Y. Sung

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.

Язык: Английский

Процитировано

2

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 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

Язык: Английский

Процитировано

5

A strategy for regioselective B–H functionalization ofo-carboranesviabase metal catalysis DOI
Jie Zhang, Zuowei Xie

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 3074 - 3079

Опубликована: Янв. 1, 2023

This frontier article summarizes the recent developments in base metal-catalyzed regioselective cage B–H functionalization of carboranes and discusses related challenging issues.

Язык: Английский

Процитировано

11

Reaction of Carboranyl Lithium and 2,3-Dichloroquinoxaline to Synthesize Carborane-Fused N-Heteroaromatic DOI
Ying Li, Peng Zhao, Caixia Jia

и другие.

Organometallics, Год журнала: 2024, Номер 43(10), С. 1077 - 1084

Опубликована: Май 16, 2024

Nucleophilic substitution of B–H is an important strategy for the synthesis carborane derivatives. Although intermolecular nucleophilic has been widely explored, intramolecular rarely reported. Herein, we synthesized a novel carborane-fused N-heteroaromatic through transition-metal-free reaction between carboranyl lithium and 2,3-dichloroquinoxaline. Two C–Cl substitutions one with were involved in this transformation. Instead most electron-deficient B(3)–H vertex, selectively occurred on B(4)–H vertex. This method provides new ring compounds.

Язык: Английский

Процитировано

3

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

Organic Letters, Год журнала: 2022, Номер 24(39), С. 7077 - 7081

Опубликована: Сен. 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.

Язык: Английский

Процитировано

13

Transition metal catalyzed selective B(3)–H or B(4)–H amination of o-carboranes via dehydrogenative BH/NH cross-coupling DOI
Hairong Lyu, Zuowei Xie

Chemical Communications, Год журнала: 2022, Номер 58(60), С. 8392 - 8395

Опубликована: Янв. 1, 2022

A unique approach to vertex-selective catalytic B-H amination at either the B(3)- or B(4)-position in o-carboranes has been developed. Using different transition metal catalysts, dehydrogenative BH/NH cross-coupling of and free amines achieved, leading a wide variety cage B(4)-aminated moderate high yields with excellent regioselectivity, where carboranyl carboxylic acids can serve as competent coupling partners without any pre-functionalization. The isolation structural identification key intermediate provide an insight into reaction mechanism B(4)-H amination.

Язык: Английский

Процитировано

12

A Pd-catalyzed route to carborane-fused boron heterocycles DOI Creative Commons

Mengjie Zhu,

Puzhao Wang,

WU Zheng-qiu

и другие.

Chemical Science, Год журнала: 2024, Номер 15(27), С. 10392 - 10401

Опубликована: Янв. 1, 2024

A Pd-catalyzed cross-coupling system has been developed to achieve vicinal diamination of 9,10-dibromo-carborane with NH-heterocycles and anilines. These products can be further converted carborane-fused six- seven-membered heterocycles.

Язык: Английский

Процитировано

2

Iridium(III)-Catalyzed Regioselective B(4)–H Amination of o-Carboranes with Sufilimines DOI

Kyeongna Park,

Gi Uk Han, S.‐K. YOON

и другие.

Organic Letters, Год журнала: 2023, Номер 25(32), С. 5989 - 5994

Опубликована: Авг. 4, 2023

Iridium(III)-catalyzed regioselective B(4)-H amination is developed from the reaction of o-carborane acids with sulfilimines without any oxidants under mild conditions, which leads to a wide range aminated o-carboranes in good yields broad substrate scope. Moreover, selective B(3,6)-diamination acid was achieved. The present attractive practical point view because dibenzothiophene quantitatively recovered and reused.

Язык: Английский

Процитировано

5

Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane DOI

Run‐Ze Yuan,

Peng‐Fei Cui,

Yue‐Jian Lin

и другие.

Chinese Journal of Chemistry, Год журнала: 2022, Номер 41(3), С. 307 - 313

Опубликована: Окт. 22, 2022

Comprehensive Summary Herein, we describe the synthesis of a carborane‐supported octanuclear palladacycle complex, Pd 8 ( o ‐C 2 B 10 H CS CH 3 ) 4 Cl (CH CN) (complex 1 ), with B(3)–H activations on ‐carborane ligand. The substitution reaction has been explored, and three its substituted complexes (L) (L = t BuNC, ; L C 5 N, S, have synthesized. m ‐ p disubstituted ligands (CS (ligands 6 as well their B—H activated carborane [ 9 PdCl] 7 ][PdCl( BuNC)] also synthesized by similar method. All these characterized, including X‐ray single crystal diffraction, NMR spectroscopy, IR spectroscopy elemental analysis methods.

Язык: Английский

Процитировано

8

Ruthenium‐Catalyzed Selective B(4)‐H Amidation of o‐Carboranes with Dioxazolones DOI
Heejin Yang, Hee Chan Noh, Phil Ho Lee

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2022, Номер 12(3)

Опубликована: Дек. 21, 2022

Abstract A ruthenium‐catalyzed selective B4 amidation of o ‐carboranes with a variety alkyl‐, aryl‐, and heteroaryl‐substituted dioxazolones is developed by carboxylic acid‐assisted B(4)‐H bond activation in ‐carborane acids, affording multitude (4)‐amidated good yields the evolution carbon dioxide. In addition, two‐fold decarboxylative reaction cage was accomplished.

Язык: Английский

Процитировано

8