8-Aminoquinoline as a bidentate traceless directing group for Cu-catalyzed selective B(4,5)–H disulfenylation ofo-carboranes

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(85), P. 12997 - 13000

Published: Jan. 1, 2020

A traceless bidentate directing group guided copper catalyzed direct cage B(4,5)-H disulfenylation of o-carboranes has been achieved, leading to a series B(4,5)-disulfenylated o-carborane derivatives in high yields with excellent regioselectivity. The situ departure the 8-aminoquinoline auxiliary circumvents additional processes for removal, thus enhancing atom-/step-economy.

Language: Английский

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A strategy for regioselective B–H functionalization ofo-carboranesviabase metal catalysis

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3074 - 3079

Published: Jan. 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7646 - 7652

Published: April 23, 2025

Language: Английский

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Post-coordination of Ru(II) Controlled Regioselective B(4)–H Acylmethylation of o-Carboranes with Sulfoxonium Ylides

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

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Palladium Catalyzed Selective B(3)–H Activation/Oxidative Dehydrogenative Coupling for the Synthesis of Bis(o-carborane)s

Inorganic Chemistry, Journal Year: 2020, Volume and Issue: 59(23), P. 17340 - 17346

Published: Nov. 24, 2020

A palladium catalyzed selective B(3)-H activation/oxidative dehydrogenative coupling for the synthesis of bis(o-carborane)s connected with B(3)-B(3') and B(3)-B(6') bonds has been developed first time. plausible mechanism involving stepwise activation B(3'/6')-H by PdII PdIV was proposed. This work is example most efficient protocol bonds, which important reference design, synthesis, application in related fields.

Language: Английский

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Catalytic Cage BH Functionalization of Carboranes via “Cage Walking” Strategy

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(4), P. 2134 - 2140

Published: Feb. 3, 2021

Carboranes, three-dimensional analogues of benzene, are finding a wide variety applications ranging from functional materials to pharmaceuticals, which has drawn tremendous research interest. The recent development transition-metal-catalyzed cage B–H functionalization can realize series vertex-specific carboranes, the "cage-walking" strategy provide BH at different positions where initial bond activation occurs achieve functionalized carboranes that difficult access by conventional methods. In this Viewpoint, we will discuss concept cage-walking and its application in selective highlighting typical examples, could some valuable insights into future carborane multifunctionalization.

Language: Английский

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Selective B(5,8,9)-Triarylation Reaction of o-Carboranes through Determination of the Order of Introduction of Aryl Groups into B(4)-Acylamino-o-carboranes

Organic Letters, Journal Year: 2021, Volume and Issue: 23(4), P. 1188 - 1193

Published: Feb. 4, 2021

Palladium-catalyzed iterative cage B–H arylation reaction of a wide range B(4)-acylamino-o-carboranes with aryl iodides has been developed, leading to the formation B(5,8,9)-triarylated excellent regioselectivity. Moreover, carboranes bearing three different groups were synthesized from B(4)-acylamino-o-carborane and iodides. The order introduction [B(9) > B(8) B(5)] into B(5,8,9)-triarylation was determined for first time through NMR monitoring X-ray analyses.

Language: Английский

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Couple-close construction of non-classical boron cluster-phosphonium conjugates

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 11, 2024

Language: Английский

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Rh‐Catalyzed Decarbonylative Cross‐Coupling between o‐Carboranes and Twisted Amides: A Regioselective, Additive‐Free, and Concise Late‐Stage Carboranylation

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(8), P. 2699 - 2706

Published: Sept. 24, 2020

Abstract The convenient cross‐coupling of sp 2 or 3 carbons with a specific boron vertex on carborane cage represents significant synthetic values and insurmountable challenges. In this work, we report an Rh‐catalyzed reaction between o ‐carborane N ‐acyl‐glutarimides to construct various B −C bonds. Under the optimized condition, removable imine directing group (DG) leads B(3)− B(3,6)−C couplings, while pyridyl DG B(3,5)−Ar coupling. particular, unexpected rearrangement amide reagent is observed in directed B(4)−C(sp ) formation. This scalable protocol has many advantages, including easy access, use cheap widely available coupling agents, no requirement external ligand, base oxidant, high efficiency, broad substrate scope. Leveraging Rh I dimer twisted amides, method enables straightforward access diversely substituted therapeutically important derivatives at site, provides highly valuable vista for carborane‐based drug screening.

Language: Английский

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Progress in the medicinal chemistry of organoboron compounds

Russian Chemical Reviews, Journal Year: 2020, Volume and Issue: 90(4), P. 451 - 487

Published: Nov. 3, 2020

The review aims to draw attention the latest advances in organoboron chemistry and therapeutic use of compounds. synthetic strategies towards boron-containing compounds with proven vitro and/or vivo biological activities, including derivatives boronic acids, benzoxaboroles, benzoxaborines benzodiazaborines, are summarized. Approaches synthesis hybrid structures containing an moiety as one pharmacophores considered, effect this modification on pharmacological activity initial molecules is analyzed. On basis analysis published data, most promising areas research field identified, methods synthesis, design effective agents. bibliography includes 246 references.

Language: Английский

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