Synthesis of Chiral, Fused Tricyclic Molecules by Sequential Metal‐Catalyzed Reactions of Simple Substrates

Saltó, Joan; Biosca, Maria; Pàmies, Òscar; Diéguez, Montserrat

doi:10.1002/adsc.202200685

Cited by 3 publications

(1 citation statement)

References 53 publications

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“…Following on from this, with the same family of ligands, the authors also used two‐step sequential reactions to obtain a set of chiral complex fused‐tricyclic compounds containing several functional groups and multiple stereogenic centers (Scheme 5 and 6). [25] In this case, they combined the Pd‐AAS of 5‐ to 8‐membered cyclic allylic substrates with a diastereoselective transformation to synthesize a range of cyclopentenone‐ and cyclobutene‐based tricyclic compounds. Again, a Pauson‐Khand transformation is used to form cyclopentenone containing compounds (Scheme 5).…”

Section: Application Of the Best Phosphite‐oxazoline Ligand Family In...mentioning

confidence: 99%

The Evolution of Phosphite‐Oxazoline Ligands for the Pd‐Allylic Substitution and Their Application in Building Chiral Molecules

et al. 2023

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Pd‐catalyzed asymmetric allylic substitution (AAS) is a highly effective method for producing chiral molecules with alkene‐substituted frameworks which can be further derivatized. However, its stereochemical outcome is affected by the steric requirements of the substrate and only a narrow set of nucleophiles yield excellent enantioselectivities. In this regard, phosphite‐oxazolines have emerged as strong candidates to be privileged ligands for this process, providing results that surpass most of the previously published studies. They have provided high enantiocontrol when used in the Pd‐AAS of several hindered and unhindered substrates, using a wide range of C‐, O‐, and N‐nucleophiles. In this concept, we review and discuss the current progress made in the design of tailor‐made phosphite‐oxazoline ligand libraries for the Pd‐AAS of a broad range of substrates and nucleophiles and its application in the construction of chiral complex molecules.

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Section: Application Of the Best Phosphite‐oxazoline Ligand Family In...mentioning

confidence: 99%

The Evolution of Phosphite‐Oxazoline Ligands for the Pd‐Allylic Substitution and Their Application in Building Chiral Molecules

et al. 2023

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Four‐Step Synthesis of (−)‐4‐epi‐Presilphiperfolan‐8α‐ol by Intramolecular Iron Hydride Atom Transfer‐Mediated Ketone‐Alkene Coupling and Studies to Accesstrans‐Hydrindanols with a Botryane Scaffold

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Gómez‐Bengoa

Bonjoch

et al. 2023

Chemistry A European J

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From an (R)‐(+)‐pulegone‐derived building block that incorporates the stereo‐defined tertiary carbon bearing a methyl group, as found in the targeted sesquiterpenoid, a four‐step synthesis of (−)‐4‐epi‐presilphiperfolan‐8‐α‐ol was achieved. The key processes involved are a ring‐closing metathesis leading to a bridged alkene‐tethered ketone and its subsequent FeIII‐mediated metal‐hydride atom transfer (MHAT) transannular cyclization. This synthetic method, implying an irreversible addition of a carbon‐centered radical upon a ketone by means of a hydrogen atom transfer upon the alkoxy radical intermediate, was also applied in the synthesis of trans‐fused hydrindanols structurally related to botrydial compounds.

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Synthesis of 1,3‐cis‐Fused Tricyclic System through Regio‐ and Stereoselective Epoxidation and Ring‐Rearrangement Metathesis: Access To Basic Core of Presilphiperfolanols

2023

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Here, we report a new synthetic approach to a highly strained 1,3-fused cis-cis-cis-5/5/6 tricyclic system that appeared among the presilphiperfolanol analogues. The cis-fusion of six-membered ring to a diquinane moiety is accomplished by substratecontrolled regio-and stereoselective epoxidation, and ringrearrangement metathesis (RRM) sequence. In this regard, both early-, and late-stage epoxidation and RRM reactions were studied. The target compound, cis-cis-cis-5/5/6 tricyclic ketone with an α,β-oxirane ring can serve as a key building block to produce various presilphiperfolanol analogues. The cis-cis-cis-5/ 5/6-tricyclic-α,β-epoxyketone can also act as masked enone and therefore useful for various chemical transformations in organic synthesis. The short synthetic sequence disclosed here may be useful to design various biologically important molecules. The newly reported molecules are well-characterized by NMR, HRMS, and IR spectral data.

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Synthesis of Chiral, Fused Tricyclic Molecules by Sequential Metal‐Catalyzed Reactions of Simple Substrates

Cited by 3 publications

References 53 publications

The Evolution of Phosphite‐Oxazoline Ligands for the Pd‐Allylic Substitution and Their Application in Building Chiral Molecules

The Evolution of Phosphite‐Oxazoline Ligands for the Pd‐Allylic Substitution and Their Application in Building Chiral Molecules

Four‐Step Synthesis of (−)‐4‐epi‐Presilphiperfolan‐8α‐ol by Intramolecular Iron Hydride Atom Transfer‐Mediated Ketone‐Alkene Coupling and Studies to Accesstrans‐Hydrindanols with a Botryane Scaffold

Synthesis of 1,3‐cis‐Fused Tricyclic System through Regio‐ and Stereoselective Epoxidation and Ring‐Rearrangement Metathesis: Access To Basic Core of Presilphiperfolanols

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