Merging Johnson-Claisen and Aromatic Claisen [3,3]-Sigmatropic Rearrangements: Ytterbium Triflate/2,6-Di-tert-butylpyridine Catalytic System

Viktoria A. Ikonnikova; Ekaterina A. Zhigileva; Amir M. Al Mufti; Pavel N. Solyev; Mikhail S. Baranov; Andrey A. Mikhaylov

doi:10.1021/acs.joc.3c00368

Merging Johnson-Claisen and Aromatic Claisen [3,3]-Sigmatropic Rearrangements: Ytterbium Triflate/2,6-Di-tert-butylpyridine Catalytic System

Viktoria A. Ikonnikova, Ekaterina A. Zhigileva, Amir M. Al Mufti, Pavel N. Solyev, Mikhail S. Baranov, Andrey A. Mikhaylov^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

General synthetic approach toward phenols with a polyfunctional side-chain is described. It is based on two subsequent [3,3]-sigmatropic rearrangements, in particular, Johnson-Claisen and aromatic Claisen. Facilitation of the reaction sequence is achieved by the separation of steps and discovery of the efficient catalysts for aromatic Claisen rearrangement. The best performance was achieved by the combination of rare earth metal triflate with 2,6-di-tert-butylpyridine. The reaction scope was established on 16 examples with 17-80% yield (on two steps). Synthetic equivalents for the related Ireland-Claisen and Eschenmoser Claisen/Claisen rearrangements were proposed. Further versality of the products was demonstrated by a number of post-modification transformations.

Original language	English
Pages (from-to)	9737-9749
Number of pages	13
Journal	Journal of Organic Chemistry
Volume	88
Issue number	14
DOIs	https://doi.org/10.1021/acs.joc.3c00368
Publication status	Published - 21 Jul 2023
Externally published	Yes

Funding

The authors gratefully acknowledge support from the Russian Science Foundation, grant No 21-73-00165.

All Science Journal Classification (ASJC) codes

Organic Chemistry

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10.1021/acs.joc.3c00368

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title = "Merging Johnson-Claisen and Aromatic Claisen [3,3]-Sigmatropic Rearrangements: Ytterbium Triflate/2,6-Di-tert-butylpyridine Catalytic System",

abstract = "General synthetic approach toward phenols with a polyfunctional side-chain is described. It is based on two subsequent [3,3]-sigmatropic rearrangements, in particular, Johnson-Claisen and aromatic Claisen. Facilitation of the reaction sequence is achieved by the separation of steps and discovery of the efficient catalysts for aromatic Claisen rearrangement. The best performance was achieved by the combination of rare earth metal triflate with 2,6-di-tert-butylpyridine. The reaction scope was established on 16 examples with 17-80% yield (on two steps). Synthetic equivalents for the related Ireland-Claisen and Eschenmoser Claisen/Claisen rearrangements were proposed. Further versality of the products was demonstrated by a number of post-modification transformations.",

author = "Ikonnikova, {Viktoria A.} and Zhigileva, {Ekaterina A.} and {Al Mufti}, {Amir M.} and Solyev, {Pavel N.} and Baranov, {Mikhail S.} and Mikhaylov, {Andrey A.}",

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year = "2023",

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day = "21",

doi = "10.1021/acs.joc.3c00368",

language = "English",

volume = "88",

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journal = "Journal of Organic Chemistry",

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TY - JOUR

T1 - Merging Johnson-Claisen and Aromatic Claisen [3,3]-Sigmatropic Rearrangements

T2 - Ytterbium Triflate/2,6-Di-tert-butylpyridine Catalytic System

AU - Ikonnikova, Viktoria A.

AU - Zhigileva, Ekaterina A.

AU - Al Mufti, Amir M.

AU - Solyev, Pavel N.

AU - Baranov, Mikhail S.

AU - Mikhaylov, Andrey A.

PY - 2023/7/21

Y1 - 2023/7/21

N2 - General synthetic approach toward phenols with a polyfunctional side-chain is described. It is based on two subsequent [3,3]-sigmatropic rearrangements, in particular, Johnson-Claisen and aromatic Claisen. Facilitation of the reaction sequence is achieved by the separation of steps and discovery of the efficient catalysts for aromatic Claisen rearrangement. The best performance was achieved by the combination of rare earth metal triflate with 2,6-di-tert-butylpyridine. The reaction scope was established on 16 examples with 17-80% yield (on two steps). Synthetic equivalents for the related Ireland-Claisen and Eschenmoser Claisen/Claisen rearrangements were proposed. Further versality of the products was demonstrated by a number of post-modification transformations.

AB - General synthetic approach toward phenols with a polyfunctional side-chain is described. It is based on two subsequent [3,3]-sigmatropic rearrangements, in particular, Johnson-Claisen and aromatic Claisen. Facilitation of the reaction sequence is achieved by the separation of steps and discovery of the efficient catalysts for aromatic Claisen rearrangement. The best performance was achieved by the combination of rare earth metal triflate with 2,6-di-tert-butylpyridine. The reaction scope was established on 16 examples with 17-80% yield (on two steps). Synthetic equivalents for the related Ireland-Claisen and Eschenmoser Claisen/Claisen rearrangements were proposed. Further versality of the products was demonstrated by a number of post-modification transformations.

UR - http://www.scopus.com/inward/record.url?scp=85164666221&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.3c00368

DO - 10.1021/acs.joc.3c00368

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SN - 0022-3263

VL - 88

SP - 9737

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 14

ER -

Merging Johnson-Claisen and Aromatic Claisen [3,3]-Sigmatropic Rearrangements: Ytterbium Triflate/2,6-Di-tert-butylpyridine Catalytic System

Abstract

Funding

All Science Journal Classification (ASJC) codes

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