The total synthesis of (+)-elaeokanidine A: natural product or isolation artefact?

Cuthbertson, James D.; Unsworth, William P.; Moody, Catherine L.; Taylor, Richard J. K.

doi:10.1016/j.tetlet.2014.12.021

Cited by 10 publications

(4 citation statements)

References 20 publications

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“…However, the authors noted that the conditions employed for the conversion of grandisine D ( 105 ) to grandisine B ( 106 ) were extremely close to the conditions used during the isolation and therefore questioned if grandisine B ( 106 ) was an artefact generated during the isolation process rather than a natural product. Similar concerns were raised during the total synthesis of (+)-elaeokanidine A ( 108 ), a structurally related indolizidine natural product, originating from the same plant family as grandisine B and D. 41 In contrast to Taylor’s previously developed approach, the synthetic route proceeded through phenylthioalkyne 102 , which allowed conversion of carbonyl–alkyne metathesis product 104 to enone 107 in 83% yield via a Liebeskind-Srogl coupling. Treatment of 107 with aqueous ammonia resulted in the expected double conjugate addition and provided a mixture of three isomers in 51% combined yield.…”

Section: Carbonyl–alkyne Metathesismentioning

confidence: 96%

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Beyond olefins: new metathesis directions for synthesis

2018

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Section: Carbonyl–alkyne Metathesismentioning

confidence: 96%

“…Total synthesis of grandisine B ( 106 ) and D ( 105 ) and elaeokanidine A ( 108 ) (Taylor and co-workers, 2011 and 2015). 40–41 …”

Section: Figurementioning

confidence: 99%

Beyond olefins: new metathesis directions for synthesis

2018

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“…However, none of the desired hydroazulenone 8 was detected. Alternatively, attempting to use a formic acid-promoted cyclization 60,61 between the thioalkyne and the acetal motifs in compound 9 returned only messy mixtures. It was postulated that the desired cyclization was prevented by the steric bulk at C-8 (caldaphnidine J numbering).…”

Section: Retrosynthetic Analysis As Shown Inmentioning

confidence: 99%

Asymmetric total synthesis of yuzurimine-type Daphniphyllum alkaloid (+)-caldaphnidine J

Guo

Zhang

et al. 2020

Nat Commun

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Ever since Hirata's report of yuzurimine in 1966, nearly fifty yuzurimine-type alkaloids have been isolated, which formed the largest subfamily of the Daphniphyllum alkaloids. Despite extensive synthetic studies towards this synthetically challenging and biologically intriguing family, no total synthesis of any yuzurimine-type alkaloids has been achieved to date. Here, the first enantioselective total synthesis of (+)-caldaphnidine J, a highly complex yuzuriminetype Daphniphyllum alkaloid, is described. Key transformations of this approach include a highly regioselective Pd-catalyzed hydroformylation, a samarium(II)-mediated pinacol coupling, and a one-pot Swern oxidation/ketene dithioacetal Prins reaction. Our approach paves the way for the synthesis of other yuzurimine-type alkaloids and related natural products.

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“…Acid-catalyzed metathesis of an alkyne and an aldehyde suitably positioned within one molecular framework is a useful way to make synthetically useful carbo- or heterocycles . Despite many reaction conditions developed for inter- and intramolecular alkyne carbonyl metathesis (ACM), to the best of our knowledge, only a few examples where ACM is applied to the total synthesis of natural products have been disclosed . As shown in Scheme a, we recently demonstrated highly efficient assembly of 3-acylchromene 2 from 1 by this protocol in the course of our total synthesis of brazilin .…”

Section: Introductionmentioning

confidence: 99%