TY - JOUR

T1 - Oxonium Ylides Generated from 1,4-Disubstituted α-Diazo Glutaconimides

T2 - a Rich Source of Diverse Oxygen Heterocyclic Frameworks

AU - Guranova, Natalia

AU - Dar'in, Dmitry

AU - Kantin, Grigory

AU - Krasavin, Mikhail

N1 - Funding Information: This research was supported by the Russian Foundation for Basic Research (project grant 21‐53‐12001). We are grateful to the Research Centre for Magnetic Resonance, the Centre for Chemical Analysis and Materials Research, and the Centre for X‐ray Diffraction Methods of Saint Petersburg State University Research Park for the analytical data. Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/6/17

Y1 - 2021/6/17

N2 - An underexplored type of heterocyclic α-diazocarbonyl compounds, α-diazo glutaconimides was involved in the generation of oxonium ylide species by Rh(II) catalysis in the presence of tetrahydrofuran and 1,4-dioxane. The formation of a spirocycle through a formal Stevens-type O→C [1,2]-shift within the oxonium ylide species in the case of THF was low-yielding and was accompanied by the known formal O→O [1,4]-shift to give fused bicyclic products. Reactions with 1,4-dioxane proved noticeably higher-yielding with respect to the target spirocycle. In this case, however, the observed by-products resulted from hitherto not described alternative formal O→C [1,4]-shift accompanied by the transposition of the double bond. The latter fate of the oxonium ylide species, although minor, is likely attributable to the unique nature of α-diazo glutaconimides as precursors to Rh(II) carbenes and subsequently formed oxonium ylide.

AB - An underexplored type of heterocyclic α-diazocarbonyl compounds, α-diazo glutaconimides was involved in the generation of oxonium ylide species by Rh(II) catalysis in the presence of tetrahydrofuran and 1,4-dioxane. The formation of a spirocycle through a formal Stevens-type O→C [1,2]-shift within the oxonium ylide species in the case of THF was low-yielding and was accompanied by the known formal O→O [1,4]-shift to give fused bicyclic products. Reactions with 1,4-dioxane proved noticeably higher-yielding with respect to the target spirocycle. In this case, however, the observed by-products resulted from hitherto not described alternative formal O→C [1,4]-shift accompanied by the transposition of the double bond. The latter fate of the oxonium ylide species, although minor, is likely attributable to the unique nature of α-diazo glutaconimides as precursors to Rh(II) carbenes and subsequently formed oxonium ylide.

KW - Heterocyclic diazo compounds

KW - Oxonium ylides

KW - Rh(II) carbenes

KW - Spirocycles

KW - Stevens rearrangement

KW - CARBENOID MEDIATED CYCLIZATIONS

KW - INSERTION

KW - MACROCYCLES

KW - CATALYST

KW - OXETANES

KW - MEDIUM-SIZED RINGS

KW - REARRANGEMENT

KW - EXPANSION

KW - CHEMISTRY

KW - DERIVATIVES

UR - http://www.scopus.com/inward/record.url?scp=85108294888&partnerID=8YFLogxK

U2 - 10.1002/ejoc.202100515

DO - 10.1002/ejoc.202100515

M3 - Article

AN - SCOPUS:85108294888

VL - 2021

SP - 3411

EP - 3420

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 23

ER -