Stereoselective Total Synthesis of the Non‐Contiguous Polyketide Natural Product (–)‐Dolabriferol

Gantasala, Naresh; Suresh, Borra; Srihari, P.

doi:10.1002/ejoc.201701748

Cited by 5 publications

(1 citation statement)

References 42 publications

(32 reference statements)

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“…Final deprotection of the alloc group (TPPS = 3,3 ,3"-phosphinidynetris(benzenesulfonic acid) trisodium salt) and formation of the cyclic hemiacetal gave (-)-dolabriferol (Scheme 7). [96] Since this first total synthesis which established the absolute configuration of (-)-dolabriferol, several other synthetic approaches have been proposed, sometimes requiring more steps [57,[97][98][99][100]. Scheme 7.…”

Section: First Total Asymmetric Synthesis Of (-)-Dolabriferolmentioning

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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Section: First Total Asymmetric Synthesis Of (-)-Dolabriferolmentioning

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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Synthesis of C₁−C₉ and C₁₀−C₂₁ Fragments of (−)‐Dolabriferol

Bandaru

Kaliappan

2020

Asian J Org Chem

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Our efforts on the synthesis of C1−C9 and C10−C21 subunits of dolabriferol, a non‐contiguous polypropionate marine natural product, from a common intermediate using two non‐aldol variants is reported. i) Shimizu reaction, a Pd(0) mediated stereoselective epoxy‐ring opening of alkenyl oxiranes, has been employed for the stereoselective installation of methyl groups at C4 and C13 and ii) Bode's protocol, a NHC‐mediated reaction on β‐epoxy aldehydes, has been utilized for stereoselective construction of methyl and hydroxyl groups in anti‐fashion at C6−C7 and C15−C16 in the natural product.

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Diastereoselective Aldol Reactions

Kennington

Costa

Romea

et al. 2024

Comprehensive Chirality

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Stereoselective Total Synthesis of the Non‐Contiguous Polyketide Natural Product (–)‐Dolabriferol

Cited by 5 publications

References 42 publications

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

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

Synthesis of C₁−C₉ and C₁₀−C₂₁ Fragments of (−)‐Dolabriferol

Diastereoselective Aldol Reactions

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Stereoselective Total Synthesis of the Non‐Contiguous Polyketide Natural Product (–)‐Dolabriferol

Cited by 5 publications

References 42 publications

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

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

Synthesis of C1−C9 and C10−C21 Fragments of (−)‐Dolabriferol

Diastereoselective Aldol Reactions

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Synthesis of C₁−C₉ and C₁₀−C₂₁ Fragments of (−)‐Dolabriferol