Asymmetric Oxidative Dearomatization Reaction

Uyanik, Muhammet; Ishihara, Kazuaki

doi:10.1002/9783527698479.ch6

Cited by 22 publications

(11 citation statements)

References 89 publications

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“…, a similar result was also observed by Xu et al in their recent synthesis of atropurpuran), , which prevented extensive studies because of insufficient materials. Most importantly, preliminary inspections revealed that an asymmetric oxidative dearomatization/IMDA cascade to access enantioenriched 6 would be difficult to achieve, thereby leading us to seek new solutions to an enantioselective total synthesis of the arcutine-type C 20 -diterpenoid alkaloids.…”

Section: Results and Discussionmentioning

confidence: 99%

Enantioselective Total Synthesis of (−)-Arcutinine

et al. 2019

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The first total synthesis of an arcutine-type C20-diterpenoid alkaloid arcutinine has been achieved in both racemic and asymmetric forms. Construction of the C4 quaternary center and the pyrrolidine E ring in an early stage proved to be important for achieving the successful synthesis of the target alkaloid. Strategically, an asymmetric conjugate addition/aldol cascade and a decarboxylative allylation reaction allowed the establishment of the vicinal all-carbon quaternary stereocenters at C4 and C5. Furthermore, a sequence consisting of an intramolecular aza-Wacker cyclization, an oxidative dearomatization/intramolecular Diels–Alder cycloaddition cascade, and a ketyl-olefin cyclization enabled the assembly of the core structure and led to the total synthesis of arcutinine.

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Section: Results and Discussionmentioning

confidence: 99%

Enantioselective Total Synthesis of (−)-Arcutinine

et al. 2019

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“…The oxidative dearomatization of phenols and their analogues has been a useful synthetic method and has been used for the syntheses of natural products or biologically active compounds . Recently, Ishihara, Uyanik, and colleagues reported the oxidative dearomatization of phenols using NaOCl·5H 2 O crystals as oxidants (Scheme ).…”

Section: Miscellaneous Reactionsmentioning

confidence: 99%

Sodium Hypochlorite Pentahydrate Crystals (NaOCl·5H₂O): A Convenient and Environmentally Benign Oxidant for Organic Synthesis

Kirihara

Okada

Sugiyama

et al. 2017

Org. Process Res. Dev.

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The novel oxidant of sodium hypochlorite pentahydrate (NaOCl·5H2O) crystals is now available for industrial and laboratory use. It is superior to conventional aqueous sodium hypochlorite solutions (aq. NaOCl). The crystalline material is 44% NaOCl and contains minimal amounts of sodium hydroxide and sodium chloride, and the aqueous solution, which is prepared from NaOCl·5H2O and water, has a pH of 11–12. Examples of the selective organic synthesis using NaOCl·5H2O involve the oxidations of primary and secondary alcohols, selective oxidations to sulfoxide and sulfone, oxidative cleavage of disulfide to sulfonyl chloride and bromide, oxaziridine synthesis, and oxidative dearomatization of phenols.

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“…Chemical dearomatizations have evolved into a powerful strategy for the construction of more complex, saturated synthetic building blocks from readily available starting materials . While most arene dearomatizations enable the installation of high-value functionalities that retain the core carbon framework, the initiation of a ring fragmentation cascade to assemble architecturally distinct scaffolds is substantially less common.…”

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A Phosphine-Mediated Dearomative Skeletal Rearrangement of Dianiline Squaraine Dyes

et al. 2021

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A phosphorus(III)-mediated dearomatization of ortho-substituted dianiline squaraine dyes results in an unusual skeletal rearrangement to provide exotic, highly conjugated benzofuranone and oxindole scaffolds bearing a C3 side chain comprised of a linear conflagration of an enol, a phosphorus ylide, and 2,4-disubstituted aniline. Employing experimental and computational analysis, a mechanistic evaluation revealed a striking dependence on the acidity of the aniline ortho substituent. Notably, the rearrangement adducts underwent rapid and complete reversion to the parent squaraine in the presence of a Brønsted acid.

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Asymmetric Oxidative Dearomatization Reaction

Cited by 22 publications

References 89 publications

Enantioselective Total Synthesis of (−)-Arcutinine

Enantioselective Total Synthesis of (−)-Arcutinine

Sodium Hypochlorite Pentahydrate Crystals (NaOCl·5H₂O): A Convenient and Environmentally Benign Oxidant for Organic Synthesis

A Phosphine-Mediated Dearomative Skeletal Rearrangement of Dianiline Squaraine Dyes

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Asymmetric Oxidative Dearomatization Reaction

Cited by 22 publications

References 89 publications

Enantioselective Total Synthesis of (−)-Arcutinine

Enantioselective Total Synthesis of (−)-Arcutinine

Sodium Hypochlorite Pentahydrate Crystals (NaOCl·5H2O): A Convenient and Environmentally Benign Oxidant for Organic Synthesis

A Phosphine-Mediated Dearomative Skeletal Rearrangement of Dianiline Squaraine Dyes

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Sodium Hypochlorite Pentahydrate Crystals (NaOCl·5H₂O): A Convenient and Environmentally Benign Oxidant for Organic Synthesis