Synthesis of (±)-hirsutene by a catalytic allylpalladium-alkyne cyclization/carbonylation cascade

Oppolzer, Wolfgang; Robyr, Chantal

doi:10.1016/s0040-4020(01)80764-x

Cited by 50 publications

(17 citation statements)

References 53 publications

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“…The gem -dimethylcyclopentane motif, which differentiates these from previous synthetic isoquinolines, is ubiquitous in natural products (cf. hirsutene, pentalenene, and the isoquinoline illudinine) but conspicuously absent from most synthetic pharmaceutical screening libraries. The rigid, hydrophobic topology of gem -dimethylcyclopentanes (cf.…”

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confidence: 99%

Thermal Cycloisomerization of Putative Allenylpyridines for the Synthesis of Isoquinoline Derivatives

2016

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confidence: 99%

Thermal Cycloisomerization of Putative Allenylpyridines for the Synthesis of Isoquinoline Derivatives

2016

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“…The total synthesis started with preparation of the intermediate C from commercially available 3,3‐dimethylglutaric anhydride D using modified procedures from the literature preparation . (Scheme ) 3,3‐Dimethylglutaric anhydride was reduced twice to the lactol 3 , and Wittig olefination of the lactol 3 produced the conjugate ester 4 .…”

Section: Resultsmentioning

confidence: 99%

“…For the synthesis of the substrate A , rather than following the reported synthetic route[5b] we adopted Pd catalyzed cycloaddition reaction route that eliminated protection‐deprotection steps from the previous synthetic route to A , since compound A could readily be prepared from bicyclic ketone C that was the known compound synthesized from commercially available D via Pd mediated cycloaddition reaction . (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

A Total Synthesis of (±)‐Ceratopicanol via Palladium Catalyzed Reductive Cyclization

Kim

Lee

et al. 2020

Eur J Org Chem

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“…57,58 For reasons explained in the introduction the asymetric synthesis of hirsutene were not dealt with here. 59 The "metallo ene reaction-carboxylation" cascade strategy 60 was left aside for saving space.…”

Section: Hirsutene (Schemes 9-26)mentioning

confidence: 99%

Information Theory Description of Synthetic Strategies in the Polyquinane Series. The Holosynthon Concept

et al. 1998

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Information theory makes it possible to give a semiquantitative graphical representation of the various strategies used to reach a given synthetic target. Skeletal complexity and similarity of the precursors with respect to the target structure provide figures which monitor the progress made from the starting material en route toward the target. Examples selected from the triquinane family are used to illustrate the benefits but also the present limits of such an approach. Whereas for silphinene and hirsutene various synthetic strategies appear in a clear graphical form when treated within this framework, coriolin shows that the skeleton-only approach provides graphics which can be misleading. To improve this limitation, progress will have to be made in the treatment of functional complexity from a synthetic point of view. From a more general point of view, a practical treatment of stereochemistry within the information theory framework is still waited for. The graphical treatment displays clearly the key step(s) in a given strategy. Such steps are often characterized by a large change in complexity and/or similarity. This semiquantitative representation converges with, on one hand, the interest of some rearrangements in shorter synthesis and, on the other hand, the interest and the limits of the class of reactions variously christened as cascades, domino, tandem. The treatment shows also the indissociable counterpart of these reaction-centered approaches: the structural entities which make them possible. Such structural entities (holosynthons) call attention to synthetic strategies where a global part (holos: whole) of the target is looked at, this view complements the more classical bond by bond, disconnection approach.Chemists have had intuitive feelings about molecular complexity. In 1981 Bertz 1 developed a quantitative approach based on information theory 2 and graph representation of molecules. 3 In this approach, the molecular complexity is measured as a function of the number and nature of its constitutive atoms and of the number and nature of the constitutive bonds. The overall complexity of the molecule is calculated as being the sum of complexities associated with connectivity factors and complexities associated with the presence of heteroatoms. Hendrickson and Toczko 4 have developed a simple algorithm for calculating this complexity for any organic compound. The results converge with a chemist's intuition on many structural features: a cyclic compound is considered more complex than its acyclic counterpart; a ramified hydrocarbon is more complex than its linear counterpart; a molecule with several carbons replaced by heteroatoms is more complex.The virtue of this approach is to provide figures allowing easy graphical comparisons of synthetic strategies. We have used it here as a convenient tool for such comparisons. Figure 1 shows on simple examples the convergence of its results with chemical intuition. Its systematic application will also reveal its limits in the analysis to come. If these limits ...

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Synthesis of (±)-hirsutene by a catalytic allylpalladium-alkyne cyclization/carbonylation cascade

Cited by 50 publications

References 53 publications

Thermal Cycloisomerization of Putative Allenylpyridines for the Synthesis of Isoquinoline Derivatives

Thermal Cycloisomerization of Putative Allenylpyridines for the Synthesis of Isoquinoline Derivatives

A Total Synthesis of (±)‐Ceratopicanol via Palladium Catalyzed Reductive Cyclization

Information Theory Description of Synthetic Strategies in the Polyquinane Series. The Holosynthon Concept

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