Quaternary Ammonium Salts: Catalysts for Hydrosilylation of Alkynes with Hydrosilanes

Andoh, Hidehiro; Nakamura, Kôsuke; Nakazawa, Yusuke; Ikeda-Fukazawa, Tomoko; Okabayashi, Satoki; Tsuchimoto, Teruhisa

doi:10.1002/adsc.202300423

Cited by 3 publications

(2 citation statements)

References 101 publications

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“…In recent years, quaternary ammonium salts (QASs) have been used as solvents and immobilization media for TM-catalysts but they have garnered significant attention as organocatalysts for the hydrofunctionalization of unsaturated C-C bonds. [32][33][34][35][36][37] We previously reported an ionic liquid-catalyzed anti-Markovnikov selective hydroboration of alkenes (Figure 1b). 38 In the current work, we investigated QASs as catalysts for hydroboration of alkenes leading to Markovnikov organoboranes (Figure 1c).…”

Section: Introductionmentioning

confidence: 99%

Markovnikov Selective Hydroboration of Aryl Alkenes Catalyzed by Quaternary Ammonium Salts

Huninik,

Im,

Szyling

et al. 2024

Preprint

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Despite recent advancements in the development of catalytic Markovnikov-selective hydroboration of alkenes, the metal-free procedure has long remained an unsolved challenge. Here, we report an organocatalytic Markovnikov-selective hy-droboration of aryl alkenes using a commercially available quaternary ammonium catalyst. The method is operationally simple, scalable, and compatible with a wide variety of substrates and it can be successfully applied in the synthesis of active pharmaceutical ingredients (API) such as Chlorphenoxamine. Through in-depth experimental and DFT studies, we elucidate a nuanced understanding of the mechanism and regioselectivity of this reaction.

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Section: Introductionmentioning

confidence: 99%

Markovnikov Selective Hydroboration of Aryl Alkenes Catalyzed by Quaternary Ammonium Salts

Huninik,

Im,

Szyling

et al. 2024

Preprint

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“…Combined with alkynes, quaternary ammonium fluoride or hydroxide salts ( n -Bu 4 NX, X = F, OH) were described to promote the heterocyclization of acetylenic derivatives in basic conditions, raising the underlying question of the activation of a triple bond by noncovalent interactions (NCIs) …”

Section: Introductionmentioning

confidence: 99%

Intra- and Intermolecular Cation–π Interactions between Onium Salts and Alkynes/Acetylene: Experimental and Theoretical Insights

Fressigné,

Jean,

Sanselme

et al. 2023

J. Org. Chem.

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Cation–π interactions between various onium salts, alkynes, and acetylene were studied, taking into account the substituents of the triple bond, the nature of the anions, and the polarity of the solvent, through a combination of MP2 calculations and experiments. In an intramolecular setting, these data (including single-crystal X-ray crystallography) concurred with the stability of folded conformers of alkynyl onium salts, even substituted with electron-withdrawing groups. To examine the contribution of these interactions on the alkyne electronic population, a thorough in silico study was carried out using natural bonding orbital analysis of the conformers. Intramolecular interactions from sulfonium salt tethered to phenylalkyne were highlighted, as illustrated above by the computed folded conformation (MP2) along with noncovalent interaction (NCI) analysis. Furthermore, investigations of intermolecular interactions, involving acetylene or phenylacetylene with various onium ions, revealed the high energy interactions of their complexes with phenyldimethylsulfonium chloride, as illustrated above with the complex PhCCH/PhMe2SCl (MP2 calculations and NCI analysis).

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Discussion Addendum for: Indium‐Catalyzed Heteroaryl–Heteroaryl Bond Formation through Nucleophilic Aromatic Substitution: Preparation of 2‐Methyl‐3‐(thien‐2‐yl)‐1H‐indole

Tsuchimoto

2024

Organic Syntheses

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One of the most frequently utilized strategies for constructing bonds on heteroaryl scaffolds is transition metal catalysis, where diverse types of bonds can now be constructed on heteroaryl rings. Another option for functionalizing heteroaryl rings is the nucleophilic aromatic substitution reaction. The C–C bond cleavage is observed during the indium‐catalyzed three‐component alkylation of pyrroles or indoles with alkynes or carbonyl compounds and nucleophiles. The electron‐rich compound that is next focused on is an amine, thereby allowing the synthesis of a broad range of heteroarylamines. This chapter describes Nitrogen–Heteroaryl Bond‐Forming reaction followed by Carbon–Heteroaryl Bond‐Forming Annulation. The chemistry of the indium–heteroarene π‐complex can be further applied to a distinct type of reaction: indium‐catalyzed formal N‐arylation and N‐alkylation of pyrroles. This transformation involves a unique nitrogen–nitrogen exchange strategy, or in other words, a pyrrole‐ring opening–closing strategy.

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Quaternary Ammonium Salts: Catalysts for Hydrosilylation of Alkynes with Hydrosilanes

Cited by 3 publications

References 101 publications

Markovnikov Selective Hydroboration of Aryl Alkenes Catalyzed by Quaternary Ammonium Salts

Markovnikov Selective Hydroboration of Aryl Alkenes Catalyzed by Quaternary Ammonium Salts

Intra- and Intermolecular Cation–π Interactions between Onium Salts and Alkynes/Acetylene: Experimental and Theoretical Insights

Discussion Addendum for: Indium‐Catalyzed Heteroaryl–Heteroaryl Bond Formation through Nucleophilic Aromatic Substitution: Preparation of 2‐Methyl‐3‐(thien‐2‐yl)‐1H‐indole

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