Tris(4-bromophenyl)aminium Hexachloroantimonate

Earle, Martyn J.; Vibert, Aude; Jahn, Ullrich

doi:10.1002/047084289x.rt397.pub2

Cited by 4 publications

(8 citation statements)

References 48 publications

(15 reference statements)

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“…The tris-4-bromophenylamminium cation radical (MB •+ ) is a commercially available reagent commonly used as a single-electron oxidant and/or an acid generator in various synthetic transformations, including protecting group removal ( para -methoxybenzyl ether, tetrahydropyranyl (THP) ether, dithioketal, and silyl ethers), glycosylations, and radical rearrangements, as well as in a high number of radical cation-mediated [4 + 2], [2 + 2], and [3 + 2] cycloaddition reactions . In addition, MB •+ has been shown to oxidize various tertiary amines, , electron-rich aromatics, − and enolates and to mediate Markovnikov hydration of ( E )-aryl enynes to the corresponding enones …”

Section: Resultsmentioning

confidence: 99%

“…Mechanistic Insights. MB •+ is a commercial reagent known for its dual reactivity as a single-electron oxidant 11,29 and as an acid generator. 11,13,14 Both modes of action may help to explain its reactivity.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Alternatively, MB •+ may generate acid either by counterion decomposition 11 or by hydrogen atom abstraction from a donor. 35 Replacing MB •+ SbCl 6…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…MB •+ is a commercial reagent known for its dual reactivity as a single-electron oxidant , and as an acid generator. ,, Both modes of action may help to explain its reactivity. However, neither of them is likely to occur, as discussed below.…”

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Triarylamminium Radical Cation Facilitates the Deprotection oftert-Butyl Groups in Esters, Ethers, Carbonates, and Carbamates

Hidasová

Slanina

2023

J. Org. Chem.

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We report a catalytic protocol for mild OtBu deprotection using two commercial reagents: the tris-4-bromophenylamminium radical cation, commonly known as magic blue (MB •+ ), and triethylsilane. Magic blue catalytically facilitates the cleavage of the C−O bond in tert-butyl carbamates, carbonates, esters, and ethers in a high isolated yield of up to 95%, and sacrificial triethylsilane accelerates the reaction. Without requiring high temperatures, transition metals, or strong acidic or basic catalysts, this method is suitable for structurally diverse compounds, including aliphatic, aromatic, and heterocyclic substrates.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Alternatively, MB •+ may generate acid either by counterion decomposition 11 or by hydrogen atom abstraction from a donor. 35 Replacing MB •+ SbCl 6…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Triarylamminium Radical Cation Facilitates the Deprotection oftert-Butyl Groups in Esters, Ethers, Carbonates, and Carbamates

Hidasová

Slanina

2023

J. Org. Chem.

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“…Triarylaminium radical cation salts have found use in a variety of transformations, including protecting group manipulations (PMB ether, dithioacetal, and dithioketal deprotections), glycosidation reactions of phenylseleno-and ethylthioglycosides, radical rearrangements, as well as a number of radical cation mediated pericyclic reactions including [4 + 2], 21 [2 + 2], 22 and [3 + 2] 23 cycloaddition reactions. 24 In addition, triarylaminium radical cation salts have been shown to oxidize a variety of tertiary amines and electron-rich aromatics. 25 Based on this precedent, we anticipated that triarylaminium radical cation salts might also promote the coupling of catharanthine and vindoline, leading to the generation of anhydrovinblastine (5).…”

Section: ■ Introductionmentioning

confidence: 99%

Triarylaminium Radical Cation Promoted Coupling of Catharanthine with Vindoline: Diastereospecific Synthesis of Anhydrovinblastine and Reaction Scope

Boon

Boger

2019

J. Am. Chem. Soc.

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A new triarylaminium radical cation promoted coupling of catharanthine with vindoline is disclosed, enlisting tris(4-bromophenyl)aminium hexachlororantimonate (BAHA, 1.1 equiv) in aqueous 0.05 N HCl/trifluoroethanol (1−10:1) at room temperature (25 °C), that provides anhydrovinblastine in superb yield (85%) with complete control of the newly formed quaternary C16′ stereochemistry. A definition of the scope of aromatic substrates that participate with catharanthine in the BAHA-mediated diastereoselective coupling reaction and simplified indole substrates other than catharanthine that participate in the reaction are disclosed that identify the key structural features required for participation in the reaction, providing a generalized indole functionalization reaction that bears little structural relationship to catharanthine or vindoline.

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Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

Debruyne

Borgmans

Radhakrishnan

et al. 2023

ACS Appl. Mater. Interfaces

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Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited. In this work, we report the synthesis and application of two bipyridine- or phenylpyridine-based COFs: TpBpyCOF and TpPpyCOF. Due to their good photocatalytic properties, both materials were applied as metal-free photocatalysts for the tandem aerobic oxidation/Povarov cyclization and α-oxidation of N-aryl glycine derivatives, with the bipyridine-based TpBpyCOF exhibiting the highest activity. By expanding the range of reactions that can be photocatalyzed by COFs, this work paves the way toward the more widespread application of COFs as metal-free heterogeneous photocatalysts as a convenient alternative for commonly used homogeneous (metal-based) photocatalysts.

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Tris(4-bromophenyl)aminium Hexachloroantimonate

Cited by 4 publications

References 48 publications

Triarylamminium Radical Cation Facilitates the Deprotection oftert-Butyl Groups in Esters, Ethers, Carbonates, and Carbamates

Triarylamminium Radical Cation Facilitates the Deprotection oftert-Butyl Groups in Esters, Ethers, Carbonates, and Carbamates

Triarylaminium Radical Cation Promoted Coupling of Catharanthine with Vindoline: Diastereospecific Synthesis of Anhydrovinblastine and Reaction Scope

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization

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