2,6-Di-<i>tert</i>-butyl-4-methylpyridine (DTBMP)

Balaban, Alexandrù T.

doi:10.1002/047084289x.rn00509

“…To identify whether the Lewis acidity of BF 3 itself or the enhanced Lewis acid‐assisted Brønsted acidity [38] (LBA) of the BF 3 /AcOH system plays a key role, another control experiment was performed where the proton trapping reagent DTBMP (2,6‐di‐ tert ‐butyl‐4‐methylpyridine) was added to the standard reaction mixture using 1‐octene ( 1 a ). DTBMP does not react with Lewis acids [27,39] . A product yield of 41 % for compound 2 a is found, which is similar to what is obtained without BF 3 in the reaction mixture (Table 1, entry 2).…”

Section: Resultssupporting

confidence: 78%

“…DTBMP does not react with Lewis acids. [27,39] A product yield of 41 % for compound 2 a is found, which is similar to what is obtained without BF 3 in the reaction mixture (Table 1, entry 2). As it was noticed that the strong Brønsted acidity of triflic acid also promotes the reaction (cfr.…”

Section: Methodssupporting

confidence: 80%

Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

Vanhoof,

De Smedt,

Derhaeg

et al. 2023

Angew Chem Int Ed

5

0

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1,2‐Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2‐dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom‐efficient reactant. This transition metal‐free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87%. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst‐free conditions. The synthetic method is extensively investigated with cyclic voltammetry.

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“…The resulting iminium cation VIII, upon deprotonation by a weak base, generated 1-acyloxyenamine IX, 12 of triflate, we anticipated that VIII would not release carboxylate to form the keteniminium cation but produce enamine intermediate IX, which enables installation of an acyl electrophile at the α-position of amides. We first exposed tertiary amide 1a to trifluoroacetic anhydride [TFAA (2a)] in the presence of 2,6-di-tert-butyl-4-methylpyridine [DTBMP (pK aH = 4.41)] 13 (Scheme 2a).…”

mentioning

confidence: 99%

“…We first exposed tertiary amide 1a to trifluoroacetic anhydride [TFAA ( 2a )] in the presence of 2,6-di- tert -butyl-4-methylpyridine [DTBMP (p K aH = 4.41)] (Scheme a). The basicity of this pyridine-derived weak base is not sufficient for the deprotonation of amide 1a .…”

mentioning

confidence: 99%

Chemoselective α-Trifluoroacetylation of Amides Using Highly Electrophilic Trifluoroacetic Anhydrides and 2,4,6-Collidine

Morita,

Makino,

Tsuda

et al. 2023

Org. Lett.

2

0

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Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

Vanhoof,

De Smedt,

Derhaeg

et al. 2023

Angewandte Chemie

0

View full text Add to dashboard Cite

1,2‐Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2‐dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom‐efficient reactant. This transition metal‐free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87%. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst‐free conditions. The synthetic method is extensively investigated with cyclic voltammetry.

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2,6-Di-tert-butyl-4-methylpyridine (DTBMP)

Cited by 5 publications

References 54 publications

Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

Chemoselective α-Trifluoroacetylation of Amides Using Highly Electrophilic Trifluoroacetic Anhydrides and 2,4,6-Collidine

Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

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