Preparation of 1,5-Dioxaspiro[5.5]undecan-3-one

Craig, Robert A.; Smith, Russell C.; Pritchett, Beau P.; Estipona, Benzi I.; Stoltz, Brian M.

doi:10.15227/orgsyn.093.0210

Cited by 3 publications

(2 citation statements)

References 24 publications

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“…111,115–116 Oxidative cleavage of the resultant amino alcohol product provided ketodioxanone 368 in 94% over 3 steps. Condensation of cyclohexylamine onto ketone 368 prior to deprotonation and alkylation with methyl iodide enabled selective monomethylation.…”

Section: Synthetic Studies Toward Polycyclic Furanobutenolide-derimentioning

confidence: 99%

“…Enantioselective construction of 1,3- cis -cyclopentenediol 365 began with the transketalization of tris(hydroxymethyl)aminomethane hydrochloride ( 367 ) with 1,1-dimethoxycyclohexane ( 366 ) (Scheme ). ,, Oxidative cleavage of the resultant amino alcohol product provided ketodioxanone 368 in 94% over three steps. Condensation of cyclohexylamine onto ketone 368 prior to deprotonation and alkylation with methyl iodide enabled selective monomethylation.…”

Section: Synthetic Studies Toward Polycyclic Furanobutenolide-derived...mentioning

confidence: 99%

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Polycyclic Furanobutenolide-Derived Cembranoid and Norcembranoid Natural Products: Biosynthetic Connections and Synthetic Efforts

Craig

Stoltz

2017

Chem. Rev.

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The polycyclic furanobutenolide-derived cembranoid and norcembranoid natural products are a family of congested, stereochemically complex, and extensively oxygenated polycyclic diterpenes and norditerpenes. Although the elegant architectures and biological activity profiles of these natural products have captured the attention of chemists since the isolation of the first members of the family in the 1990s, the de novo synthesis of only a single polycyclic furanobutenolide-derived cembranoid and norcembranoid has been accomplished. This article will begin with a brief discussion of the proposed biosyntheses and biosynthetic connections among the polycyclic furanobutenolide-derived cembranoids and norcembranoids followed by a comprehensive review of the synthetic efforts toward each member of the natural product family, including biomimetic, semisynthetic, and de novo synthetic strategies. This body of knowledge has been gathered in order to provide insight into the reactivity and constraints of these compact and highly oxygenated polycyclic structures, as well as to offer guidance for future synthetic endeavors.

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Section: Synthetic Studies Toward Polycyclic Furanobutenolide-derimentioning

confidence: 99%

Section: Synthetic Studies Toward Polycyclic Furanobutenolide-derived...mentioning

confidence: 99%

Polycyclic Furanobutenolide-Derived Cembranoid and Norcembranoid Natural Products: Biosynthetic Connections and Synthetic Efforts

Craig

Stoltz

2017

Chem. Rev.

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Development of a Unified Enantioselective, Convergent Synthetic Approach Toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Asymmetric Formation of the Polycyclic Norditerpenoid Carbocyclic Core by Tandem Annulation Cascade

et al. 2018

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An enantioselective and diastereoselective approach toward the synthesis of the tetracyclic scaffold of the furanobutenolide-derived polycyclic norditerpenoids is described. Focusing on synthetic efforts toward ineleganolide, the synthetic approach utilizes a palladium-catalyzed enantioselective allylic alkylation for the construction of the requisite chiral tertiary ether. A diastereoselective cyclopropanation-Cope rearrangement cascade enabled the convergent assembly of the ineleganolide [6,7,5,5]-tetracyclic scaffold. Investigation of substrates for this critical tandem annulation process is discussed along with synthetic manipulations of the [6,7,5,5]-tetracyclic scaffold and the attempted interconversion of the [6,7,5,5]-tetracyclic scaffold of ineleganolide to the isomeric [7,6,5,5]-core of scabrolide A and its naturally occurring isomers. Computational evaluation of ground-state energies of late-stage synthetic intermediates was used to guide synthetic development and aid in the investigation of the conformational rigidity of these highly constrained and compact polycyclic structures.

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Unified Enantioselective, Convergent Synthetic Approach toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Synthesis of a Series of Ineleganoloids by Oxidation-State Manipulation of the Carbocyclic Core

et al. 2019

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Late-stage synthetic efforts to advance the enatio-and diastereoselectively constructed [6,7,5,5]-fused tetracyclic scaffold toward the polycyclic norditerpenoid ineleganolide are disclosed. The described investigations focus on oxidation state manipulation around the central cycloheptane ring. Computational evaluation of ground state energies of dihydroineleganolide are used to rationalize empirical observations and provide insight for further synthetic development, enhancing the understanding of the conformational constraints of these compact polycyclic structures. Advanced synthetic manipulations generated a series of natural product-like compounds termed the ineleganoloids. Ineleganolide (1)

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Preparation of 1,5-Dioxaspiro[5.5]undecan-3-one

Abstract: Graphical abstract

Cited by 3 publications

References 24 publications

Polycyclic Furanobutenolide-Derived Cembranoid and Norcembranoid Natural Products: Biosynthetic Connections and Synthetic Efforts

Polycyclic Furanobutenolide-Derived Cembranoid and Norcembranoid Natural Products: Biosynthetic Connections and Synthetic Efforts

Development of a Unified Enantioselective, Convergent Synthetic Approach Toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Asymmetric Formation of the Polycyclic Norditerpenoid Carbocyclic Core by Tandem Annulation Cascade

Unified Enantioselective, Convergent Synthetic Approach toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Synthesis of a Series of Ineleganoloids by Oxidation-State Manipulation of the Carbocyclic Core

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