Palladium(0)‐Catalyzed Rearrangement of Allylic Esters

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Standard

Palladium(0)‐Catalyzed Rearrangement of Allylic Esters. / Jessen, Bo M.; Ondozabal, Jun Miyatake; Pedersen, Christian Marcus; Sølvhøj, Amanda; Taarning, Esben; Madsen, Robert.

I: ChemistrySelect, Bind 5, Nr. 8, 2020, s. 2559-2563.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Jessen, BM, Ondozabal, JM, Pedersen, CM, Sølvhøj, A, Taarning, E & Madsen, R 2020, 'Palladium(0)‐Catalyzed Rearrangement of Allylic Esters', ChemistrySelect, bind 5, nr. 8, s. 2559-2563. https://doi.org/10.1002/slct.v5.8

APA

Jessen, B. M., Ondozabal, J. M., Pedersen, C. M., Sølvhøj, A., Taarning, E., & Madsen, R. (2020). Palladium(0)‐Catalyzed Rearrangement of Allylic Esters. ChemistrySelect, 5(8), 2559-2563. https://doi.org/10.1002/slct.v5.8

Vancouver

Jessen BM, Ondozabal JM, Pedersen CM, Sølvhøj A, Taarning E, Madsen R. Palladium(0)‐Catalyzed Rearrangement of Allylic Esters. ChemistrySelect. 2020;5(8):2559-2563. https://doi.org/10.1002/slct.v5.8

Author

Jessen, Bo M. ; Ondozabal, Jun Miyatake ; Pedersen, Christian Marcus ; Sølvhøj, Amanda ; Taarning, Esben ; Madsen, Robert. / Palladium(0)‐Catalyzed Rearrangement of Allylic Esters. I: ChemistrySelect. 2020 ; Bind 5, Nr. 8. s. 2559-2563.

Bibtex

@article{0c7476e6d47c47adaadbfbd7591824bc,
title = "Palladium(0)‐Catalyzed Rearrangement of Allylic Esters",
abstract = "The palladium‐catalyzed transposition of allylic esters is usually performed with a rather high loading of a palladium(II) catalyst. In the present investigation, a palladium(0) catalyst is developed for rearranging methyl 2‐acyloxybut‐3‐enoates into the corresponding methyl 4‐acyloxycrotonates. The transformation is performed at room temperature with 2% of Pd(PPh3)4 and gives good yields with acetate, benzoate and propanoate esters. Methyl 2‐(methoxycarbonyloxy)but‐3‐enoate, on the other hand, is rearranged into methyl 4‐methoxycrotonate due to decarboxylation of the released methyl carbonate into methoxide. The mechanism for the transposition of methyl 2‐acetoxybut‐3‐enoate was investigated in two separate crossover experiments and shown to proceed by formation of the intermediate π‐allyl palladium(II) complex, which is then attacked by acetate in an intermolecular fashion.",
author = "Jessen, {Bo M.} and Ondozabal, {Jun Miyatake} and Pedersen, {Christian Marcus} and Amanda S{\o}lvh{\o}j and Esben Taarning and Robert Madsen",
year = "2020",
doi = "10.1002/slct.v5.8",
language = "English",
volume = "5",
pages = "2559--2563",
journal = "ChemistrySelect",
issn = "2365-6549",
publisher = "Chemistry Europe",
number = "8",

}

RIS

TY - JOUR

T1 - Palladium(0)‐Catalyzed Rearrangement of Allylic Esters

AU - Jessen, Bo M.

AU - Ondozabal, Jun Miyatake

AU - Pedersen, Christian Marcus

AU - Sølvhøj, Amanda

AU - Taarning, Esben

AU - Madsen, Robert

PY - 2020

Y1 - 2020

N2 - The palladium‐catalyzed transposition of allylic esters is usually performed with a rather high loading of a palladium(II) catalyst. In the present investigation, a palladium(0) catalyst is developed for rearranging methyl 2‐acyloxybut‐3‐enoates into the corresponding methyl 4‐acyloxycrotonates. The transformation is performed at room temperature with 2% of Pd(PPh3)4 and gives good yields with acetate, benzoate and propanoate esters. Methyl 2‐(methoxycarbonyloxy)but‐3‐enoate, on the other hand, is rearranged into methyl 4‐methoxycrotonate due to decarboxylation of the released methyl carbonate into methoxide. The mechanism for the transposition of methyl 2‐acetoxybut‐3‐enoate was investigated in two separate crossover experiments and shown to proceed by formation of the intermediate π‐allyl palladium(II) complex, which is then attacked by acetate in an intermolecular fashion.

AB - The palladium‐catalyzed transposition of allylic esters is usually performed with a rather high loading of a palladium(II) catalyst. In the present investigation, a palladium(0) catalyst is developed for rearranging methyl 2‐acyloxybut‐3‐enoates into the corresponding methyl 4‐acyloxycrotonates. The transformation is performed at room temperature with 2% of Pd(PPh3)4 and gives good yields with acetate, benzoate and propanoate esters. Methyl 2‐(methoxycarbonyloxy)but‐3‐enoate, on the other hand, is rearranged into methyl 4‐methoxycrotonate due to decarboxylation of the released methyl carbonate into methoxide. The mechanism for the transposition of methyl 2‐acetoxybut‐3‐enoate was investigated in two separate crossover experiments and shown to proceed by formation of the intermediate π‐allyl palladium(II) complex, which is then attacked by acetate in an intermolecular fashion.

U2 - 10.1002/slct.v5.8

DO - 10.1002/slct.v5.8

M3 - Journal article

VL - 5

SP - 2559

EP - 2563

JO - ChemistrySelect

JF - ChemistrySelect

SN - 2365-6549

IS - 8

ER -

ID: 238850870