Group 13 exchange and transborylation in catalysis

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 325 - 348

Опубликована: Март 21, 2023

Catalysis is dominated by the use of rare and potentially toxic transition metals. The main group offers a sustainable alternative for catalysis, due to generally higher abundance lower toxicity these elements. Group 13 elements have rich catalogue stoichiometric addition reactions unsaturated bonds but cannot undergo redox chemistry which underpins transition-metal catalysis. exchange transfer one or more groups from element another, through σ-bond metathesis; where boron both elements, this termed transborylation. These redox-neutral processes are increasingly being used render traditionally 13-mediated catalytic develop new processes, examples focus review.

Язык: Английский

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Iron(I) and Iron(II) Boxmi Pincer Complexes: Coordination Chemistry and Catalytic Hydroboration of Nitriles

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Июнь 4, 2025

Язык: Английский

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Zinc Hydride-Catalyzed Dihydroboration of Isonitriles and Nitriles: Mechanistic Studies with the Structurally Characterized Zinc Intermediates

Organometallics, Год журнала: 2023, Номер 42(16), С. 2293 - 2303

Опубликована: Авг. 16, 2023

The conjugated bis-guanidinate (CBG)-stabilized zinc hydride, [{LZnH}2; (L = {(ArNH)(ArN)–C═N–C═(NAr)(NHAr)}; Ar 2,6-Et2-C6H3)] (Zn-1), is shown to be a highly active catalyst for the double reduction of isonitriles and nitriles with pinacolborane (HBpin) in this study. A wide array nitriles, including aryl alkyl groups, underwent hydroboration afford exclusively 1,2- 1,1-diborylated amine products, respectively. series stoichiometric reactions were performed understand reaction mechanisms. Hydroboration isonitrile proceeds through formation formimidoyl complex, [LZnC(H)N(tBu)]2 (Zn-2), while nitrile vinylidenamido [LZnNC(H)(C6H5)]2 (Zn-3). Moreover, compounds Zn-2 Zn-3 are isolated thoroughly characterized. Such molecular complexes rare literature.

Язык: Английский

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Amidophosphine Boranes as Hydroboration Reagents for Nitriles, Alkynes, and Carboxylic Acids

Organic Letters, Год журнала: 2023, Номер 25(43), С. 7923 - 7927

Опубликована: Окт. 26, 2023

We report here the hydroboration of nitriles, alkynes, and carboxylic acids using amidophosphine boranes {(BH3)(PPh2)-NC(CH3)3}, {(BH3)2(PPh)2N(CH2)C6H5}, {(BH3)2(PPh2)2N-(BH3)CH2C6H4N} as reducing agents. These compounds were synthesized to replace more commonly used borane reagents. Solid boranes, which with ease, demonstrated excellent reactivity functional group tolerance toward a wide variety acids, affording corresponding ammonium salts, alkenes, alcohols in good yield.

Язык: Английский

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Mapping boron catalysis onto a phosphorus cluster platform

Dalton Transactions, Год журнала: 2022, Номер 51(47), С. 18329 - 18336

Опубликована: Янв. 1, 2022

Clusters of main group elements, such as phosphorus, arsenic, germanium, and tin - called Zintl clusters have been known for more than a century. However, their application in catalysis is largely unknown. Here, we tether boranes to seven-atom phosphorus cluster ({C8H14}BCH2CH2SiMe2)3P7 (2) demonstrate Lewis acid proof-of-principle that boron chemistry can be mapped onto using this method. Catalyst 2 was employed mediate key organic transformations, including the hydroboration carbodiimides, isocyanates, ketones, alkenes, alkynes, nitriles. To best our knowledge, first Zintl-based an innocent platform metal-free catalysis. By chaining boron, its treasure chest unlocked at these clusters. Hence, beyond method could find applications neutron capture therapy, stimuli responsive materials, cross-coupling, frustrated pair functional polymer chemistries.

Язык: Английский

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Zintl Clusters as a Platform for Lewis Acid Catalysis

Inorganic Chemistry, Год журнала: 2024, Номер 63(43), С. 20117 - 20125

Опубликована: Май 30, 2024

Clusters of the main group elements phosphorus and arsenic, commonly categorized as Zintl clusters, have been known for over a century. And, only now is application these systems catalysts organic synthesis being investigated. In this work, boranes are tethered via an aliphatic linker to Zintl-based clusters their Lewis acidity examined experimentally, by Gutmann–Beckett test competency in hydroborative reduction six substrates, well computationally, fluoride ion affinity hydride methods. The effects tuning length, substituents at boron, changing cluster from seven-atom system arsenic on reactivity studied.

Язык: Английский

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Au Nanoparticle-Catalyzed Double Hydrosilylation of Nitriles by Diethylsilane

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(26), С. 5346 - 5352

Опубликована: Янв. 1, 2024

We present the first example of Au-catalyzed reduction nitriles into primary amines. In contrast to monohydrosilanes which are completely unreactive, diethylsilane (a dihydrosilane) is capable reducing aryl or alkyl amines under catalysis by Au nanoparticles supported on TiO

Язык: Английский

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Borane-catalysed C2-selective indole reductive functionalisation

Chemical Communications, Год журнала: 2024, Номер 60(77), С. 10748 - 10751

Опубликована: Янв. 1, 2024

Indolines are common motifs within pharamceuticals and natural products. Boron catalysis enables the chemoselective allylation of indoles to give allylic indolines in excellent diastereoselectivity. Mechanistic studies revealed

Язык: Английский

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Transborylation-Enabled Boron Catalysis

Synthesis, Год журнала: 2022, Номер 55(01), С. 62 - 74

Опубликована: Окт. 10, 2022

Abstract This review highlights transborylation (controlled boron-boron exchange) and its applications as a turnover strategy in boron-catalysed methodologies. Catalytic of B–C, B–O, B–N, B–F, B–S, B–Se transborylations are discussed the context transborylation-enabled catalysis, across wide range organic transformations including hydroboration, C–C bond formation, C–H borylation, chemoselective reduction, asymmetric reduction. 1 Introduction 2 B–C Transborylation 3 B–O 4 B–N 5 B–F 6 B–S 7 Conclusion

Язык: Английский

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Room Temperature Reduction of Titanium Tetrachloride-Activated Nitriles to Primary Amines with Ammonia-Borane

Molecules, Год журнала: 2022, Номер 28(1), С. 60 - 60

Опубликована: Дек. 21, 2022

The reduction of a variety aromatic and aliphatic nitriles, activated by molar equivalent titanium tetrachloride, has been achieved at room temperature using ammonia borane as safe reductant. corresponding methanamines were isolated in good to excellent yields following simple acid-base workup.

Язык: Английский

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