Studies Toward the Synthesis of Spirolides: Assembly of the Elaborated E-Ring Fragment

Stivala, Craig E.; Zakarian, Armen

doi:10.1021/ol8027797

Cited by 30 publications

(15 citation statements)

References 45 publications

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“…As previously noticed by Ishihara10 and Brimble,8a, 11 on related compounds, the non‐natural transoid ‐ isomer is formed preferentially in all cases. All our efforts to reverse the stereocontrol upon acetalization failed whatever the conditions used.…”

Section: Resultssupporting

confidence: 71%

Synthesis of the C10–C24‐Bis‐Spiroacetal Core of 13‐Desmethyl Spirolide C Based on a Sila‐Stetter‐Acetalization Process

Labarre‐Laine

Periñán

Desvergnes

et al. 2014

Chemistry A European J

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Synthesis of the bis-spiroacetal core of 13-desmethyl spirolide C has been completed based on a sila-Stetter-acetalization process. The acylsilane and enone partners in the Stetter reaction were prepared in 7 and 11 steps, respectively, from (S) and (R)-aspartic acid. The quaternary center at C19 in the enone moiety was controlled by relying on the Seebach's chiral self-reproduction method using an enantiopure (S)-lactic acid based dioxolanone. The final acid-catalyzed spiroacetalization provided the desired spiroacetal as a mixture of diastereoisomers in 13 linear steps. Whatever the conditions used, the non-natural transoid isomer was formed preferentially. However, both cisoid and transoid isomers were isolated pure and their structure assigned unambiguously through NMR spectroscopic studies.

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Section: Resultssupporting

confidence: 71%

Synthesis of the C10–C24‐Bis‐Spiroacetal Core of 13‐Desmethyl Spirolide C Based on a Sila‐Stetter‐Acetalization Process

Labarre‐Laine

Periñán

Desvergnes

et al. 2014

Chemistry A European J

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“…In the latter study, the fully elaborated precursor to the spiroimine was constructed by a highly diastereoselective Ireland-Claisen rearrangement (Scheme 6). 86 The reaction established the quaternary center at the core of the spiroimine ring system along with other stereochemical features. The product was advanced to a 23-membered macrocyclic intermediate incorporating most of the structural information of the spirolides; however, the ring-closing metathesis in the last step of the sequence proved to be challenging.…”

Section: Synthetic Chemistry and Chemical Stability Of CI Toxinsmentioning

confidence: 98%

Synthesis and biology of cyclic imine toxins, an emerging class of potent, globally distributed marine toxins

et al. 2015

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From a small group of exotic compounds isolated only two decades ago, Cyclic Imine (CI) toxins have become a major class of marine toxins with global distribution. Their distinct chemical structure, biological mechanism of action, and intricate chemistry ensures that CI toxins will continue to be the subject of fascinating fundamental studies in the broad fields of chemistry, chemical biology, and toxicology. The worldwide occurrence of potent CI toxins in marine environments, their accumulation in shellfish, and chemical stability are important considerations in assessing risk factors for human health. This review article aims to provide an account of chemistry, biology, and toxicology of CI toxins from their discovery to the present day.

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“…This approach was applied to the synthesis of the natural product (+)‐pinnatoxin A and a fragment of spirolide C . In these particular two cases, a Koga‐type chiral lithiated base was used to obtain the stereodefined polysubstituted enolate, therefore ensuring the efficiency of the subsequent rearrangement.…”

Section: Sigmatropic Rearrangementsmentioning

confidence: 99%

Synthesis of Enantioenriched Vicinal Tertiary and Quaternary Carbon Stereogenic Centers within an Acyclic Chain

2019

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Overcoming the inherent difficulty to prepare quaternary carbon stereogenic centers, the diastereo‐ and enantioselective preparation of acyclic carbon backbones possessing vicinal quaternary and tertiary stereogenic centers (i.e. in a 1,2‐relationship) causes distorted geometries and represents a very acute problem in organic synthesis. Several approaches are discussed in this minireview underlining the challenges illustrated by the rather limited number of approaches available to practitioners.

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Studies Toward the Synthesis of Spirolides: Assembly of the Elaborated E-Ring Fragment

Cited by 30 publications

References 45 publications

Synthesis of the C10–C24‐Bis‐Spiroacetal Core of 13‐Desmethyl Spirolide C Based on a Sila‐Stetter‐Acetalization Process

Synthesis of the C10–C24‐Bis‐Spiroacetal Core of 13‐Desmethyl Spirolide C Based on a Sila‐Stetter‐Acetalization Process

Synthesis and biology of cyclic imine toxins, an emerging class of potent, globally distributed marine toxins

Synthesis of Enantioenriched Vicinal Tertiary and Quaternary Carbon Stereogenic Centers within an Acyclic Chain

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