A Total Synthesis of Epothilones Using Solid‐Supported Reagents and Scavengers

Storer, Richard; Takemoto, Tsunematsu; Jackson, Patrick N. Wyse; Ley, Steven V.

doi:10.1002/ange.200351413

Cited by 16 publications

(6 citation statements)

References 70 publications

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“…Therefore, we employed a two-step Peterson olefination procedure as described by Ley and co-workers. [61] The addition of a commercially available Grignard reagent and subsequent treatment with BF 3 ·OEt 2 triggered the desired elimination reaction and afforded compound 91 on a multigram scale. Moreover, only a single chromatographic purification step was needed.…”

Section: Synthesis Of Amino Alcohol 13mentioning

confidence: 99%

Modular Total Synthesis of Rhizopodin: A Highly Potent G‐Actin Dimerizing Macrolide

Kretschmer

Dieckmann

et al. 2013

Chemistry A European J

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A highly convergent total synthesis of the potent polyketide macrolide rhizopodin has been achieved in 29 steps by employing a concise strategy that exploits the molecule's C2 symmetry. Notable features of this convergent approach include a rapid assembly of the macrocycle through a site-directed sequential cross-coupling strategy and the bidirectional attachment of the side chains by means of Horner-Wadsworth-Emmons (HWE) coupling reactions. During the course of this endeavor, scalable routes for synthesis of three main building blocks of similar complexity were developed that allowed for their stereocontrolled construction. This modular route will be amenable to the development of syntheses of other analogues of rhizopodin.

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Section: Synthesis Of Amino Alcohol 13mentioning

confidence: 99%

Modular Total Synthesis of Rhizopodin: A Highly Potent G‐Actin Dimerizing Macrolide

Kretschmer

Dieckmann

et al. 2013

Chemistry A European J

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“…The synthesis of fragment 9 started with the protection of the known chiral ester 4 as its triethylsilyl (TES) ether, followed by treatment of the methyl ester with trimethylsilylmethyllithium to give methyl ketone 6 in 83 % yield over two steps (Scheme ). Treatment of ketone 6 with KHMDS and N ‐phenyltrifluoromethanesulfonimide afforded enol triflate 7 in 91 % yield.…”

Section: Resultsmentioning

confidence: 99%

Discovery, Total Synthesis and Key Structural Elements for the Immunosuppressive Activity of Cocosolide, a Symmetrical Glycosylated Macrolide Dimer from Marine Cyanobacteria

Gunasekera

Ratnayake

et al. 2016

Chemistry A European J

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A new dimeric macrolide xylopyranoside, cocosolide (1), was isolated from the marine cyanobacterium preliminarily identified as Symploca sp. from Guam. The structure was determined by a combination of NMR, HRMS, X-ray diffraction studies and Mosher’s analysis of the base hydrolysis product. Its carbon skeleton closely resembles that of clavosolides A–D isolated from the sponge Myriastra clavosa, for which no bioactivity is known. We performed the first total synthesis of cocosolide (1) along with its [α,α]-anomer (26) and macrocyclic core (28), thus leading to the confirmation of the structure of natural 1. The convergent synthesis featured Wadsworth–Emmons cyclopropanation, Sakurai annulation, Yamaguchi macrocyclization/dimerization reaction, α-selective glycosidation and β-selective glycosidation. Compounds 1 and 26 potently inhibited IL-2 production in both T-cell receptor dependent and independent manners. Full activity requires the presence of the sugar moiety as well as the intact dimeric structure. Cocosolide (1) also suppressed the proliferation of anti-CD3-stimulated T-cells in a dose-dependent manner.

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“…They interact with microtubules in the same fashion as Taxol-type compounds, causing fast and effective cellular death. Several total syntheses have been reported to date. − One of the most convergent strategies was designed by Taylor and Chen using NHTK as the key step to link fragments C7–C12 and C13–C21 . The reaction between 34 and 35 worked with exceptional yield, delivering allylic alcohol 36 without any kind of stereoselectivity.…”

Section: Uses Of the Nhtk Reaction In Total Synthesismentioning

confidence: 99%

Role of the Nozaki–Hiyama–Takai–Kishi Reaction in the Synthesis of Natural Products

2017

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The Nozaki-Hiyama-Takai-Kishi (NHTK) reaction was discovered in the late 1970s and, since then, its main application has been its use in total synthesis. In this comprehensive review, the efficiency of the NHKT reaction in the synthesis of a great number of different scaffolds present in complex natural products is analyzed. The preparation of enol and allylic and propargylic alcohol motifs is discussed, highlighting factors such as yield, chemoselectivity, stereoselectivity, or the importance of protecting groups. The review is divided into two main sections: intermolecular and intramolecular NHTK reactions. A final discussion about the current "state-of-art" and future perspectives for the use of this transformation in total synthesis is also included.

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A Total Synthesis of Epothilones Using Solid‐Supported Reagents and Scavengers

Cited by 16 publications

References 70 publications

Modular Total Synthesis of Rhizopodin: A Highly Potent G‐Actin Dimerizing Macrolide

Modular Total Synthesis of Rhizopodin: A Highly Potent G‐Actin Dimerizing Macrolide

Discovery, Total Synthesis and Key Structural Elements for the Immunosuppressive Activity of Cocosolide, a Symmetrical Glycosylated Macrolide Dimer from Marine Cyanobacteria

Role of the Nozaki–Hiyama–Takai–Kishi Reaction in the Synthesis of Natural Products

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