Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex

White, James D.; Jensen, Mark S.

doi:10.1021/ja00128a008

Cited by 74 publications

(26 citation statements)

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“…The use of the Shiina reagent23 can sometimes suppress this isomerization, so we first tried esterification under the preferred conditions for macrolactonization. Alcohol 28 (1 equiv) and acid 27 (2 equiv) were reacted with the Shiina reagent (4 equiv) in the presence of excess Et 3 N and DMAP (Scheme 6).…”

Section: Resultsmentioning

confidence: 99%

Streamlined Syntheses of (−)-Dictyostatin, 16-Desmethyl-25,26-dihydrodictyostatin, and 6-epi-16-Desmethyl-25,26-dihydrodictyostatin

et al. 2010

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The dictyostatins are a promising class of potential anticancer drugs because they are powerful microtubule stabilizing agents, but the complexity of their chemical structures is a severe impediment to their further development. Based on both synthetic and medicinal chemistry analyses, 25,26-dihydro-16-desmethyldictyostatin and its C6 epimer were chosen as potentially potent yet accessible dictyostatin analogs, and three new syntheses were developed. A relatively classical synthesis involving vinyllithium addition and macrocyclization gave way to a newer and more practical approach based on esterification and ring-closing metathesis reaction. Finally, aspects of these two approaches were combined to provide a third new synthesis based on esterification and Nozaki-Hiyama-Kishi reaction. This was used to prepare the target dihydro analogs and the natural product. All of the syntheses are streamlined because of their high convergence. The work provided several new analogs of dictyostatin including a truncated macrolactone and a C10 E-alkene, which were 400-fold and 50-fold less active than (−)-dictyostatin. In contrast, the targeted 25,26-dihydro-16-desmethyldictyostatin analogs retained almost complete activity in preliminary biological assays.

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Section: Resultsmentioning

confidence: 99%

Streamlined Syntheses of (−)-Dictyostatin, 16-Desmethyl-25,26-dihydrodictyostatin, and 6-epi-16-Desmethyl-25,26-dihydrodictyostatin

et al. 2010

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“…A precise definition of the term has been offered by Gerwick who views the class of oxylipins as those substances 'formed from fatty acids by reaction(s) involving at least one step of mono-or dioxygenase oxidation.' 2 This expression permits the inclusion of compounds of varying chain length, typically C 16 to C 22 , and replaces the narrower version that restricted oxylipins to C 20 icosanoids derived from arachidonic acid (1) (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

White¹,

Yang²

2009

Synlett

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Biomimetic and other strategies that have been developed in the author's laboratory for the synthesis of a subset of the group of enzymically oxidized lipids known as oxylipins are described. This set of oxylipins contains both a cyclopropane and a lactone, with the lactone ring size varying between six and nine members. A biomimetic approach employing cascade cyclization of an epoxyalkenoic acid was successful in creating the cyclopropane and six-membered lactone of C 20 oxylipins such as the constanolactones in a single step, but failed in an attempt to create the ninemembered lactone of halicholactone. Solandelactones, C 22 oxylipins containing a cyclopropane and an eight-membered lactone, were synthesized by directed Simmons-Smith cyclopropanation followed by Claisen rearrangement of a cyclic ketene acetal to construct the lactone

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“…It consists in the retrosynthetic cleavage of the structure into the two synthons A and В, the coupling of which by the Kishi-Nozaki 5 reaction is a relatively easy solving problem. [4][5][6][7] Recently, we have developed an enantiodirected biomimetic method for the preparation of synthon of the type B (see Refs 8 and 9). Preparation of chiral synthons of the type A was the following problem.…”

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confidence: 99%

Enantioselective synthesis of (1E,3S)-1-iodoundec-1-en-5-yn-3-ol, the eicosanoid synthon

2009

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Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex

Cited by 74 publications

References 0 publications

Streamlined Syntheses of (−)-Dictyostatin, 16-Desmethyl-25,26-dihydrodictyostatin, and 6-epi-16-Desmethyl-25,26-dihydrodictyostatin

Streamlined Syntheses of (−)-Dictyostatin, 16-Desmethyl-25,26-dihydrodictyostatin, and 6-epi-16-Desmethyl-25,26-dihydrodictyostatin

Strategies for the Synthesis of the Cyclopropyl-Substituted Lactone Family of Oxylipins

Enantioselective synthesis of (1E,3S)-1-iodoundec-1-en-5-yn-3-ol, the eicosanoid synthon

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