Retro‐Friedel‐Crafts‐Type Acidic Ring‐Opening of Triptycenes: A New Synthetic Approach to Acenes

Iwata, Tomonori; Kawano, Ryusei; Fukami, Takuto; Shindo, Mitsuru

doi:10.1002/chem.202104160

Cited by 4 publications

(3 citation statements)

References 66 publications

(3 reference statements)

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“…29 Overall, this data confirmed that the generation of 6 from 3 (cf. Table 2) likely proceeds via an intermolecular retro-Friedel Crafts/Friedel-Crafts process 30 and not an intramolecular rearrangement.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Neocannabinoids Using Controlled Friedel-Crafts Reactions

Millimaci

Trilles

McNeely

et al. 2023

Preprint

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A simple, one-step transformation to produce 8,9-dihydrocannabidiol (H2CBD) and related “neocannabinoids” via controlled Friedel-Crafts reactions is reported. Experimental and computational studies probing the mechanism of neocannabinoid synthesis from cyclic allylic alcohol and substituted resorcinol reaction partners provide understanding of the kinetic and thermody-namic factors driving regioselectivity for the reaction. Herein, we present a reaction scope for neocannabinoid synthesis including the production of both normal and abnormal isomers under both kinetic and thermodynamic control. Discovery and optimization of this one-step protocol between various allylic alcohols and resorcinol derivatives is discussed and supported with density-functional theory (DFT) calculations.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of Neocannabinoids Using Controlled Friedel-Crafts Reactions

Millimaci

Trilles

McNeely

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Overall, this data confirmed that the generation of 3 from 6 ( cf. Table ) likely proceeds via an intermolecular retro-Friedel Crafts/Friedel–Crafts process and not an intramolecular rearrangement pathway.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Neocannabinoids Using Controlled Friedel–Crafts Reactions

Millimaci,

Trilles,

McNeely

et al. 2023

J. Org. Chem.

View full text Add to dashboard Cite

A one-step transformation to produce 8,9-dihydrocannabidiol (H 2 CBD) and related "neocannabinoids" via controlled Friedel−Crafts reactions is reported. Experimental and computational studies probing the mechanism of neocannabinoid synthesis from cyclic allylic alcohol and substituted resorcinol reaction partners provide understanding of the kinetic and thermodynamic factors driving regioselectivity for the reaction. Herein, we present the reaction scope for neocannabinoid synthesis including the production of both normal and abnormal isomers under both kinetic and thermodynamic control. Discovery and optimization of this onestep protocol between various allylic alcohols and resorcinol derivatives are discussed and supported with density functional theory calculations.

show abstract

“…Friedel–Crafts condensations are reversible, as evidenced by the degradation of the triarylmethane intermediates in the presence of acid. 32 Precipitation from the reaction medium drives reaction progression and contributes to the near quantitative yields. For more soluble intermediates, like 13, performing the reaction under an inert atmosphere improves the yield, by avoiding premature oxidation to the final rhodamine, which would otherwise complicate purification at this stage ( Table 1 ).…”

Section: Resultsmentioning

confidence: 99%