Total Synthesis of the Potent Antitumor Macrolides Pladienolide B and D

Kanada, Regina Mikie; Itoh, Daisuke; Nagai, Mitsuo; Niijima, Jun; Asai, Naoki; Mizui, Yoshiharu; Abe, Shinya; Kotake, Yoshihiko

doi:10.1002/anie.200604997

Cited by 90 publications

(62 citation statements)

References 62 publications

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“…4.1.11. (2S,3R,E)-5-((4R,5R)-5-((4-methoxybenzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)pent-4-ene-2,3-diyl diacetate 18 To a cooled (0°C) solution of diol 17 (520 mg, 1.47 mmol) in CH 2 Cl 2 (15 mL) were added triethylamine (0.83 ml, 5.9 mmol), acetic anhydride (0.42 mL, 4.43 mmol), and a catalytic amount of DMAP and stirred at room temperature for 6 h. After completion of the reaction, the reaction was diluted with aqueous NaHCO 3 (5 mL) and extracted into DCM (2 Â 30 mL). The combined organic phase was washed with brine, and dried over Na 2 SO 4 .…”

Section: (6r7se)-ethyl 67-bis(tert-butyldimethylsilyloxy)oct-2-en-mentioning

confidence: 99%

Total synthesis of synargentolide B

Ramulu

Rajaram

Dasari

et al. 2015

Tetrahedron: Asymmetry

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Section: (6r7se)-ethyl 67-bis(tert-butyldimethylsilyloxy)oct-2-en-mentioning

confidence: 99%

Total synthesis of synargentolide B

Ramulu

Rajaram

Dasari

et al. 2015

Tetrahedron: Asymmetry

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“…These examples used a less efficient RCM but a better catalyst loading was employed (Scheme 5.11) [33].…”

Section: Other Antibiotic Macrolidesmentioning

confidence: 99%

Synthesis of Natural Products Containing Macrocycles by Alkene Ring‐Closing Metathesis

Gradillas¹,

Pérez‐Castells²

2010

Metathesis in Natural Product Synthesis

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IntroductionThe impact of metathesis in modern synthetic chemistry is evidenced by the number of publications and reviews that have appeared in the last decade, some of them covering the specific field of macrocyclization in natural product synthesis [1]. It is therefore difficult not to repeat the reports done by other authors or duplicate their critical views on the chemistry. This chapter is exclusively devoted to the total syntheses of natural bioactive macrocycles involving diene and the diene-ene metathesis, and focuses on the reaction conditions used in the macrocyclization key step and on the stereochemical outcome of the reaction. As we shall see, the choice of the catalyst, solvent, temperature, concentration, and reaction time is crucial in these transformations. In addition, we show how subtle variations on the structure of the substrate lead to modifications in the conformational organization of the molecule, which are critical for the success of ring-closing metathesis (RCM). In particular, the substitution pattern, the steric hindrance of the substituents, the ring size to be formed, and the presence of coordinating heteroatoms are particularly important as they have an important influence on the outcome of the reaction. This chapter has been organized around the various families of natural products in order to compare the reaction conditions for compounds bearing structural similarities. We have deliberately decided to reveal only the information regarding the metathesis step and thus not disclose other details of the syntheses.Synthetic efforts toward macrocycles are often laborious and unpractical. The classical strategies involved are macrolactonizations, macrolactamizations, and macroaldolizations. The macrocyclization approach encounters several problems including the competition between the desired intramolecular reaction and intermolecular processes, which result in the formation of polymers. RCM has the advantage of being compatible with a wide variety of functional groups and forming double bonds that can eventually be converted into other functionalities. The main disadvantages are the control of the stereochemistry of the newly formed double bond and the optimization of the yield. On the other hand, the concomitant loss of ethylene makes this reaction highly atom economical and entropically Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts. Edited by

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“…It appears that the epoxidation is compatible with several functional groups such as the benzimidazole in 61, and the existing ketone in the macrocycle did not appear to interfere with the epoxidation [51,52]. In their synthesis of pladienolide B (65) (potent antitumor agent) (Scheme 3.23), Kotake and coworkers recently reported that sulfone 63 was epoxidized with ketone 42 in 71% yield and >99% de after recrystallization, and the resulting epoxide was then attached to the macrocylic ring via Julia-Kocienski alkenation [53].…”

Section: ) [24f ] Such Interactions Are Also Supported Bymentioning

confidence: 99%

Organocatalytic Oxidation. Ketone‐Catalyzed Asymmetric Epoxidation of Alkenes and Synthetic Applications

Shi

2010

Modern Oxidation Methods

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The asymmetric epoxidation of alkenes constitutes a powerful approach to enantiomerically enriched epoxides, a class of highly versatile intermediates in organic synthesis [1]. Various effective epoxidation systems have been developed, including epoxidation of allylic [2, 3] and homoallylic [4] alcohols, metal-catalyzed epoxidation of unfunctionalized alkenes [5][6][7], and the nucleophilic epoxidation of electron-deficient alkenes [8]. During the past 10-15 years, much effort has been devoted to chiral ketone-catalyzed asymmetric epoxidation (Scheme 3.1). The subject has been described in great detail in the first edition [9] and other reviews [10]. This chapter provides an update on progress in this area since the first edition [9].Scheme 3.1 Chiral ketone-catalyzed asymmetric epoxidation of alkenes.Modern Oxidation Methods. Edited by Jan-Erling Bäckvall

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Total Synthesis of the Potent Antitumor Macrolides Pladienolide B and D

Cited by 90 publications

References 62 publications

Total synthesis of synargentolide B

Total synthesis of synargentolide B

Synthesis of Natural Products Containing Macrocycles by Alkene Ring‐Closing Metathesis

Organocatalytic Oxidation. Ketone‐Catalyzed Asymmetric Epoxidation of Alkenes and Synthetic Applications

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