Mixed Bioengineering–Chemical Synthesis Approach for the Efficient Preparation of Δ7-Dafachronic Acid

Kinzurik, Matias I.; Hristov, Lachezar V.; Matsuda, Seiichi P. T.; Ball, Zachary T.

doi:10.1021/ol5006642

Cited by 8 publications

(1 citation statement)

References 37 publications

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“…In parallel to the aforementioned strategy, an olefin cross-metathesis of ( S )-β-citronellol with ethyl or methyl methacrylate was also investigated as strategy 3 (Scheme and Table ). Although this transformation has been already exploited with terpenoid derivatives to the best of our knowledge, it has not been used to synthesize any of the desired 2,6-dimethyloctane C10 chirons. A first attempt with ethyl methacrylate, based upon the conditions described by Bruneau et al , gave α,β-unsaturated ester 9a with 52% conversion (estimated by 1 H NMR).…”

Section: Resultsmentioning

confidence: 99%

Straightforward Synthesis of Chiral Terpenoid Building Blocks by Ru-Catalyzed Enantioselective Hydrogenation

et al. 2021

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Starting from commercially available (R)-and (S)-β-citronellol, two strategies were designed to synthesize all four stereoisomers of 2,6-dimethyloctane monoterpene chirons in four or five steps in 32−47% overall yield. The desired fragments were obtained by a key Ru-catalyzed asymmetric olefin hydrogenation step under moderate temperature (50 °C), pressure (4 bar), and low catalyst loadings (0.5 mol %) under optimized conditions. Screening of commercially available catalysts highlighted the key role of DM-SEGPHOS as an economically advantageous alternative to commonly used H8-BINAP for equal performances. These results open new possibilities for versatile and scalable syntheses of these useful building blocks.

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Section: Resultsmentioning

confidence: 99%

Straightforward Synthesis of Chiral Terpenoid Building Blocks by Ru-Catalyzed Enantioselective Hydrogenation

et al. 2021

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Late‐Stage Formal Double C−H Oxidation of Prenylated Molecules to Alkylidene Oxetanes and Azetidines by Strain‐Enabled Cross‐Metathesis

et al. 2023

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Prenylation is a ubiquitous late‐stage modification in nature that often confers significantly improved bioactivity for secondary metabolites. While this lipophilic modification renders enhanced potency, the lipophilic tag(s) can diminish bioavailability and adversely alter drug transportation and metabolism. Thus, a functional‐group‐tolerant, mild, and selective late‐stage C−H functionalization of prenyl tags would present a great potential in drug discovery programs but could also impact other fields, such as agrochemistry and chemical biology. Herein we report an exocyclic‐strain‐driven cross‐metathesis reaction of prenyl tags, a formal double C−H oxidation protocol, that can be used for the selective late‐stage derivatization of prenylated compounds and natural products. This methodology avoids the need for prefunctionalization of target molecules and affords ready access to an unprecedented library of oxo‐ and aza‐prenylated complex molecules. Thus, in a broader context, this methodology extends late‐stage functionalization beyond that available to nature.

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Late‐Stage Formal Double C−H Oxidation of Prenylated Molecules to Alkylidene Oxetanes and Azetidines by Strain‐Enabled Cross‐Metathesis

et al. 2023

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Prenylation is a ubiquitous late-stage modification in nature that often confers significantly improved bioactivity for secondary metabolites. While this lipophilic modification renders enhanced potency, the lipophilic tag(s) can diminish bioavailability and adversely alter drug transportation and metabolism. Thus, a functional-group-tolerant, mild, and selective latestage CÀ H functionalization of prenyl tags would present a great potential in drug discovery programs but could also impact other fields, such as agrochemistry and chemical biology. Herein we report an exocyclicstrain-driven cross-metathesis reaction of prenyl tags, a formal double CÀ H oxidation protocol, that can be used for the selective late-stage derivatization of prenylated compounds and natural products. This methodology avoids the need for prefunctionalization of target molecules and affords ready access to an unprecedented library of oxo-and aza-prenylated complex molecules. Thus, in a broader context, this methodology extends late-stage functionalization beyond that available to nature.

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Mixed Bioengineering–Chemical Synthesis Approach for the Efficient Preparation of Δ7-Dafachronic Acid

Cited by 8 publications

References 37 publications

Straightforward Synthesis of Chiral Terpenoid Building Blocks by Ru-Catalyzed Enantioselective Hydrogenation

Straightforward Synthesis of Chiral Terpenoid Building Blocks by Ru-Catalyzed Enantioselective Hydrogenation

Late‐Stage Formal Double C−H Oxidation of Prenylated Molecules to Alkylidene Oxetanes and Azetidines by Strain‐Enabled Cross‐Metathesis

Late‐Stage Formal Double C−H Oxidation of Prenylated Molecules to Alkylidene Oxetanes and Azetidines by Strain‐Enabled Cross‐Metathesis

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