Photocatalyst-free, visible-light-induced regio- and stereoselective synthesis of phosphorylated enamines from N-allenamides via [1,3]-sulfonyl shift at room temperature DOI Creative Commons
Jia‐Dong Guo, Feven-Alemu Korsaye, Dorian Schutz

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(43), P. 17962 - 17970

Published: Jan. 1, 2024

Herein, we report the first visible-light-induced strategy for rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- stereoselective manner from N -sulfonyl allenamides H-phosphine oxides.

Language: Английский

Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer DOI Creative Commons
Filip S. Meger, John A. Murphy

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

Citations

30

Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

Citations

15

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

Minghui Zhu,

Herman H. Y. Sung

et al.

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

Published: Jan. 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.

Language: Английский

Citations

2

Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters DOI
Hongyuan Ren, Ningning Zhou, Wenli Ma

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

The innovation of synthetic strategies for selective B-H functionalization is a pivotal objective in the realm boron cluster chemistry. However, precise, efficient, and rapid bond carboranes that distant from existing functional groups remains intractable owing to limited approaches site-selective control established methods. Herein, we report dative bonding activation strategy nonclassical remote site

Language: Английский

Citations

8

Photocatalytic [3 + 2]-annulation via sodium tetraarylborate: a fundamental approach for synthesizing 1,4,2-diazaborole analogs DOI Creative Commons

Hao-Ni Qin,

Haowen Jiang, Yi Zhao

et al.

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

Published: Jan. 1, 2025

Nitriles stabilize neutral diarylboryl radicals, generating the RCN-BAr 2 complex, an efficient boron-nitrogen synthon that reacts with imines and olefins for photocatalytic synthesis of boron–nitrogen heterocycles, such as 1,4,2-diazaboroles.

Language: Английский

Citations

1

A variable bidentate traceless directing group for nickel-catalyzed regioselective B–H poly-chalcogenation of o-carboranes DOI
Ping Li, Zaozao Qiu, Jian Lu

et al.

Inorganic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A nickel-catalyzed direct cage B–H poly-chalcogenation of icosahedral carborane clusters, enabled by a variable bidentate 8-aminoquinoline traceless directing group, has been developed under oxidant-free and weakly basic conditions.

Language: Английский

Citations

1

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

Jiarui Chang,

Hou‐Ji Cao, Yan‐Na Ma

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

Citations

1

Visible‐Light‐Induced Photoreduction of Carborane Phosphonium Salts: Efficient Synthesis of Carborane‐Oxindole‐Pharmaceutical Hybrids DOI Open Access
Qiang Liu,

Bei‐Bei Zhang,

Sheng He

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: April 29, 2023

Visible-light-induced photoreaction of carboranes is an effective approach to prepare carborane-containing compounds. While several methods involving boron-centered carboranyl radicals have been established, those for carbon-centered are underdeveloped, except the UV-light-promoted photohomolysis. Herein, we describe a simple but access by photoreduction carborane phosphonium salts under blue light irradiation without using transition metals and photocatalysts. The utility method was demonstrated successfully preparing range carborane-oxindole-pharmaceutical hybrids radical cascade reactions. Computational experimental studies suggest that generated single-electron transfer photoactive charge-transfer complexes between additive potassium acetate.

Language: Английский

Citations

13

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

3

Pd(II)-catalyzed B(9)-alkynylation of o/m-carboranes DOI
Haotian Zhang, Yan Gao, Yan‐Na Ma

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6706 - 6711

Published: Jan. 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.

Language: Английский

Citations

3