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

J Org Chem. 2023 Jul 21;88(14):9737-9749. doi: 10.1021/acs.joc.3c00368. Epub 2023 Jun 29.

Authors

Viktoria A Ikonnikova^{1

2}, Ekaterina A Zhigileva^{1

3}, Amir M Al Mufti^{1

2}, Pavel N Solyev⁴, Mikhail S Baranov^{1

5}, Andrey A Mikhaylov^{1

6}

Affiliations

¹ Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry of the Russian Academy of Sciences, 16/10 Miklukho-Maklaya Street, Moscow 117997, Russia.
² D.I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya sq., Moscow 125047, Russia.
³ Chemical Department, Moscow State University, 1 Leninskie Gory, Moscow 119991, Russia.
⁴ Engelhardt Institute of Molecular Biology of the Russian Academy of Sciences, 32 Vavilova Street, Moscow 119991, Russia.
⁵ Pirogov Russian National Research Medical University, 1 Ostrovityanova Street, Moscow 117997, Russia.
⁶ National Research University Higher School of Economics, 20 Myasnitskaya Street, Moscow 101000, Russia.

PMID: 37382499
DOI: 10.1021/acs.joc.3c00368

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.