Dearomative [2 + 1] Spiroannulation of Bromophenols with Electron-Deficient Alkenes

A base-assisted dearomative [2 + 1] spiroannulation of p/o-bromophenols with activated olefins (methylenemalonates) to construct various cyclopropyl spirocyclohexadienone skeletons is reported. Furthermore, several other halophenols (X = Cl, I) were also tolerated in this process. Control experiment...

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Published inJournal of organic chemistry Vol. 89; no. 11; pp. 8041 - 8054
Main Authors Yang, Ting-Ting, Zhang, Yun-Qiao, Xie, Ming-Sheng, Tian, Yin, Wang, Dong-Chao, Guo, Hai-Ming
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 17.05.2024
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
DUOCARMYCINS
ANNULATION
NATURAL-PRODUCTS
CATALYTIC ASYMMETRIC DEAROMATIZATION
CONSTRUCTION
ALLYLIC DEAROMATIZATION
DNA ALKYLATION PROPERTIES
CC-1065
QUATERNARY CENTERS
CYCLIZATION
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Summary:A base-assisted dearomative [2 + 1] spiroannulation of p/o-bromophenols with activated olefins (methylenemalonates) to construct various cyclopropyl spirocyclohexadienone skeletons is reported. Furthermore, several other halophenols (X = Cl, I) were also tolerated in this process. Control experiments reveal a dearomative Michael addition of phenols at their halogenated positions to methylenemalonates, followed by intramolecular radical-based SRN1 dehalogenative cyclopropanation. However, according to the density functional theory (DFT) calculations, an SN2 dehalogenative cyclopropanation with the same low activation energy barrier should not be excluded. The utility of this method is showcased by gram-scale syntheses and transformations of the dearomatized products.
Bibliography:ObjectType-Article-1
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.4c00680