Synthetic studies on polypropionate antibiotics based on the stereospecific methylation of γ δ-epoxy acrylates by trimethylaluminum. A highly stereoselective construction of the eight contiguous chiral centers of ansa-chains of rifamycins

Miyashita, Masaaki; Yoshihara, Kousei; Kawamine, Katsumi; Hoshino, M.; Irie, Hiroshi

doi:10.1016/s0040-4039(00)73733-6

Cited by 27 publications

(3 citation statements)

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“…They also reported the formal synthesis of protomycinolide IV 7 [ 139 ]. In addition, several other fragments and/or natural products have been prepared by Miyashita et al For instance, the following polypropionate-containing-natural products: (−)-serricornin 23 [ 140 ], rifamycins 15 [ 141 ], streptovaricin U 16c [ 142 ], protostreptovaricin I and II ( 16c-d ) [ 142 ], scytophycin C 11 [ 143 , 144 , 145 ], swinholides A-C 14a-c [ 146 ], tedanolide 9 [ 147 ], lepranthin 8 [ 148 ], and venturicidins 10a-c [ 149 ] were all prepared from epoxides and trimethylaluminum for the regio- and stereospecific methylation ( Figure 11 , bottom). It is worth noting that Miyashita also reported the use of m -chloroperoxybenzoic acid ( m CPBA) for highly stereoselective epoxidations of chiral allylic alcohols [ 150 ] and organoselenium reagents for a chemoselective reduction of epoxides [ 151 ]; both important methodologies for the synthesis of polypropionates.…”

Section: Polypropionate Epoxide-based Approachesmentioning

confidence: 99%

Epoxide-Based Synthetic Approaches toward Polypropionates and Related Bioactive Natural Products

Rodríguez-Berríos

Isbel

Bugarin

2023

IJMS

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Polypropionate units are a common structural feature of many of the natural products in polyketides, some of which have shown a broad range of antimicrobial and therapeutic potential. Polypropionates are composed of a carbon skeleton with alternating methyl and hydroxy groups with a specific configuration. Different approaches have been developed for the synthesis of polypropionates and herein we include, for the first time, all of the epoxide-based methodologies that have been reported over the years by several research groups such as Kishi, Katsuki, Marashall, Miyashita, Prieto, Sarabia, Jung, McDonald, etc. Several syntheses of polypropionate fragments and natural products that employed epoxides as key intermediates have been described and summarized in this review. These synthetic approaches involve enatio- and diastereoselective synthesis of epoxides (epoxy-alcohols, epoxy-amides, and epoxy-esters) and their regioselective cleavage with carbon and/or hydride nucleophiles. In addition, we included a description of the isolation and biological activities of the polypropionates and related natural products that have been synthetized using epoxide-based approaches. In conclusion, the epoxide-based methodologies are a non-aldol alternative approach for the construction of polypropionate.

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Section: Polypropionate Epoxide-based Approachesmentioning

confidence: 99%

Epoxide-Based Synthetic Approaches toward Polypropionates and Related Bioactive Natural Products

Rodríguez-Berríos

Isbel

Bugarin

2023

IJMS

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“…Since then, several total asymmetric syntheses of the polypropionate fragment have been proposed [120][121][122][123]. The construction of the C 19 -C 27 fragment ((-)-48 and analogues) of this antibiotic has become a challenging target for the testing of asymmetric synthetic methods and strategies [50,[124][125][126][127][128][129][130][131][132][133][134][135][136][137][138][139][140][141].…”

Section: Expeditious Asymmetric Synthesis Of the Stereoheptad C 19 -C...mentioning

confidence: 99%

Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions

Vogel

Gonzalo

2021

Catalysts

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For a long time, the organic chemistry of sulfur dioxide (SO2) consisted of sulfinates that react with carbon electrophiles to generate sulfones. With alkenes and other unsaturated compounds, SO2 generates polymeric materials such as polysulfones. More recently, H-ene, sila-ene and hetero-Diels–Alder reactions of SO2 have been realized under conditions that avoid polymer formation. Sultines resulting from the hetero-Diels–Alder reactions of conjugated dienes and SO2 are formed more rapidly than the corresponding more stable sulfolenes resulting from the cheletropic additions. In the presence of a protic or Lewis acid catalyst, the sultines derived from 1-alkoxydienes are ionized into zwitterionic intermediates bearing 1-alkoxyallylic cation moieties which react with electro-rich alkenes such as enol silyl ethers and allylsilanes with high stereoselectivity. (C–C-bond formation through Umpolung induced by SO2). This produces silyl sulfinates that react with carbon electrophiles to give sulfones (one-pot four component asymmetric synthesis of sulfones), or with Cl2, generating the corresponding sulfonamides that can be reacted in situ with primary and secondary amines (one-pot four component asymmetric synthesis of sulfonamides). Alternatively, Pd-catalyzed desulfinylation generates enantiomerically pure polypropionate stereotriads in one-pot operations. The chirons so obtained are flanked by an ethyl ketone moiety on one side and by a prop-1-en-1-yl carboxylate group on the other. They are ready for two-directional chain elongations, realizing expeditious synthesis of long-chain polypropionates and polyketides. The stereotriads have also been converted into simpler polypropionates such as the cyclohexanone moiety of baconipyrone A and B, Kishi’s stereoheptad unit of rifamycin S, Nicolaou’s C1–C11-fragment and Koert’s C16–CI fragment of apoptolidin A. This has also permitted the first total synthesis of (-)-dolabriferol.

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“…During the mid-eighties, Lipshutz developed a reiterative route for the preparation of all- syn -1,3-polyols and polyketides, reacting optically active epoxides with higher order cis- or trans -propenyl cuprates . Later, Miyashita and co-workers developed a reiterative entry to polypropionates by means of a regio- and stereoselective methylation of γ,δ-epoxy acrylates with trimethylalane …”

Section: Introductionmentioning

confidence: 99%

Stereoselective Construction of all-anti Polypropionate Modules: Synthesis of the C5−C10 Fragment of Streptovaricin U

2009

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A concise non-aldol approach for the stereoselective construction of all-anti polypropionate fragments was developed. The iterative epoxide-based methodology consists of the syn-selective epoxidation of cis homoallylic alcohols using the VO(acac) 2 catalyzed conditions followed by epoxide cleavage with a propynyl aluminum reagent as key steps. The methodology was applied to the synthesis of the all-anti C6-C10 fragment of streptovaricin U.

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Synthetic studies on polypropionate antibiotics based on the stereospecific methylation of γ δ-epoxy acrylates by trimethylaluminum. A highly stereoselective construction of the eight contiguous chiral centers of ansa-chains of rifamycins

Cited by 27 publications

References 20 publications

Epoxide-Based Synthetic Approaches toward Polypropionates and Related Bioactive Natural Products

Epoxide-Based Synthetic Approaches toward Polypropionates and Related Bioactive Natural Products

Expeditious Asymmetric Synthesis of Polypropionates Relying on Sulfur Dioxide-Induced C–C Bond Forming Reactions

Stereoselective Construction of all-anti Polypropionate Modules: Synthesis of the C5−C10 Fragment of Streptovaricin U

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