Copper‐Catalyzed Oxidative Dearomatization of 2‐Naphthols <i>via</i> Etherification

Yi, Jiawei; Wu, Zhijie; You, Shu‐Li

doi:10.1002/cjoc.201900242

Cited by 15 publications

(4 citation statements)

References 82 publications

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“…Fortunately, the required oxidative dearomatization proceeded smoothly at ambient temperature with singlet oxygen using tetraphenylporphyrin (TPP) as the photosensitizer and 400 W sodium lamp as the light source. After consumption of the starting material, the unstable peroxy quinol intermediate was reduced by triphenylphosphine to the desired cyclohexadienone 24 .…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access to Multi-Stereocenter Cyclohexanes from a Phenol

et al. 2020

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Tiglianes such as prostratin and related diterpenoids are biologically significant natural molecules and long-standing targets for organic synthesis community. Due to the complex polycyclic scaffolds, high oxygenation level, and dense functional groups and stereocenters, their de novo chemical syntheses still face formidable challenges despite extensive efforts in the past 40 years. This account details the development of a modular and concise synthesis of prostratin, a potent anti-HIV and anticancer agent.The key approach in this synthesis involved a sequence of oxidative dearomatization and sequential stereoselective installation of peripheral groups to rapidly build the contiguously substituted cyclohexane C-ring. Inspired by Wender's work, an acid-and solventcontrolled stereodivergent formation of cyclopropane D-ring was developed. Mechanistic investigations by computational methods revealed that the competition between intra-and intermolecular hydrogen bonding led to different conformations, thus favoring different protonation processes. The designed and unexpected chemistry along this campaign reflected the uniqueness of the natural structures and should be amenable to future chemical syntheses of related complex polycyclic molecules.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access to Multi-Stereocenter Cyclohexanes from a Phenol

et al. 2020

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“…Shortly after, You and colleagues developed a copper‐catalyzed oxidative dearomatization of β‐naphthols via etherification reaction with diversely substituted naphthols 50 . The new dearomative C–O bond forming transformation resulted in a multi‐functionalized β‐naphthalenones 51 in high yield (up to 82 %, Scheme b) . It is worth of mentioning that the protocol kept its own efficiency also on the gram‐scale variant.…”

Section: Transition Metal Catalyzed Dearomatization Of Naphtholsmentioning

confidence: 97%

Recent Advances in the Catalytic Dearomatization of Naphthols

Bandini

2020

Eur J Org Chem

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The catalytic dearomatization of naphthols offers a unique platform to rapidly access structurally complex and densely functionalized molecular architectures. Thermodynamically more favorable, with respect to the analogous phenol‐variant, the transformation of the phenolic ring into the corresponding naphthalenone (cited here as naphthyl dearomatization) has faced a considerable amount of attention over the past decade with constant improvements towards stereocontrol. A collection of the most representative and recent catalytic variants involving carbon–carbon as well as carbon–heteroatom bond forming events are presented in this Minireview article.

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“…7,8 The You group has reported a copper catalyzed intermolecular oxidative dearomatization reaction of naphthols via cross-etherification using air as an oxidant (Scheme 1b). 9 This kind of reaction path is also possible in our reaction design. Diverse synthesis can be realized by a careful selection of the reaction conditions.…”

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confidence: 99%