
Research Square (Research Square), Год журнала: 2024, Номер unknown
Опубликована: Июль 24, 2024
Язык: Английский
Research Square (Research Square), Год журнала: 2024, Номер unknown
Опубликована: Июль 24, 2024
Язык: Английский
Organic Letters, Год журнала: 2023, Номер 25(25), С. 4621 - 4626
Опубликована: Июнь 15, 2023
We present here an iridium-catalyzed diastereo- and enantioselective [4 + 1] cycloaddition reaction of hydroxyallyl anilines with sulfoxonium ylides under mild conditions, leading to 3-vinyl indolines in moderate good yields excellent enantioselectivities. Control experiments disclosed a plausible mechanism.
Язык: Английский
Процитировано
13Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(24), С. 4174 - 4188
Опубликована: Дек. 1, 2022
Abstract Carboranes, a three‐dimensional class of carbon‐boron molecular clusters with remarkable electronic, physical, chemical characteristics, have proved as useful building blocks in boron neutron capture therapy agents, supramolecular design, optoelectronics, nanomaterials and organometallic/coordination chemistry. Thus, various organic modifications the B−H C−H functionalities carboranes been developed. These methods great success utilize directing groups, such carboxylic acids, to achieve selective functionalization carboranes. The carboxyl group can be easily introduced then removed after reactions. On other hand, assisted by highly regioselective electrophilic attack at electron‐rich positions B(4) B(5) cage generates five‐membered metallacyclic intermediates, which undergo further transformation. In this review, we show that transition metal‐catalyzed decarboxylation cross coupling reactions offer an opportunity for direct activation magnified image
Язык: Английский
Процитировано
18The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(4), С. 2474 - 2479
Опубликована: Фев. 2, 2024
Picolyl group directed B(3,5)-dialkenylation and B(4)-monoalkenylation of
Язык: Английский
Процитировано
3Synthesis, Год журнала: 2024, Номер unknown
Опубликована: Июнь 11, 2024
Abstract Carboranes are a type of molecular clusters consisting carbon, hydrogen, and boron atoms. They possess unique characteristics, such as three-dimensional aromaticity, icosahedral geometry, robustness. Functionalized carboranes have been utilized in various fields, including medicine, materials, organometallic/coordination chemistry. In this context, selective functionalization o-carboranes has received tremendous attention, specifically the regio- enantioselective modification ten chemically similar BH vertices within carborane cage. recent years, significant progress made catalytic vertex-specific functionalization, well achieving cage BH. This review provides an overview advancements research field. 1 Introduction 2 Carboxy-Assisted Functionalization 2.1 Formation B–C Bonds 2.2 B–N 2.3 B–O 2.4 B–X 2.5 Consecutive B–Y (Y = N, O) 3 N-Based Directing-Group-Assisted B–H 3.1 Acylamino Directing Group 3.2 Amide 3.3 Pyridyl 3.4 Imine 4 Phosphinyl-Assisted Cage 5 Bidentate-Directing-Group-Assisted 6 Other 7 Conclusions
Язык: Английский
Процитировано
3Chemical Science, Год журнала: 2025, Номер unknown
Опубликована: Янв. 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.
Язык: Английский
Процитировано
0Inorganic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 21, 2025
A transition-metal-catalyzed iterative multiple cage B-H activation reaction for constructing multifunctionalization of o-carboranes in one pot is challenging. Herein, palladium-catalyzed regioselective tetra-arylation a wide range C(1)-N-aryl-o-carboranyl amides with aryl iodides has been developed. variety B(3,4,5,6)-tetra-arylated were synthesized good-to-excellent yields. Moreover, the mono-, di-, and triarylated intermediate products isolated, exact structures determined by NMR, high-resolution mass spectrometry, X-ray analysis, which provide rationale that order introduction groups into o-carborane B(4) > B(5) B(3)/B(6). This protocol represents powerful synthetic method polyfunctionalization derivatives under very mild simple conditions, offers valuable reference design synthesis molecular propellers based on carboranes.
Язык: Английский
Процитировано
0Organic Letters, Год журнала: 2022, Номер 24(17), С. 3128 - 3133
Опубликована: Апрель 25, 2022
We disclose an iridium(III)-catalyzed regioselective B(4)-H allenylation of o-carboranes from o-carborane acids and propargyl carbonates under ball-milling conditions. This study sheds light on a novel method to accomplish B(4)-allenylation that cannot be realized through conventional solution-based reactions. Control experiments, including solution, neat, microwave, high-temperature reactions, reveal the is unique for
Язык: Английский
Процитировано
14Organic 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
13Organic Letters, Год журнала: 2023, Номер 25(36), С. 6643 - 6648
Опубликована: Авг. 30, 2023
Iridium(I)-catalyzed regioselective B(4)-alkenylation has been developed from o-carboranyl sulfoxonium ylides and alkynes through B(4)–H activation. The sequential B(4)- B(6)-alkenylation afforded B(3,5)-dialkenylated in one pot. Eventually, two alkenyl groups, the same or different, were introduced at positions 3 5 of carborane. Sulfoxonium ylide used as a directing group remains available for further functionalization is converted to B-alkenylated trichloromethyl ketones.
Язык: Английский
Процитировано
8The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 6974 - 6986
Опубликована: Май 4, 2024
A LiBr-promoted formal C(sp3)–H bond insertion reaction between β-carbonyl esters and sulfoxonium ylides is established. This practical has a wide range of substrate scope for both to give variety 1,4-dicarbonyl compounds with 43–94% yields. The features transition-metal-free conditions exclusive C-alkylation chemselectivity. use bench-stable overcomes previous methods that require transition metal as catalysts unstable diazo or toxic haloketones alkylation reagents.
Язык: Английский
Процитировано
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