Enantioenriched aryne atropisomers having a biaryl stereogenic axis vicinal to the reactive triple bond are demonstrated to exist. These reaction intermediates are easily produced in situ and can undergo the standard aryne cycloaddition chemistry in an enantiospecific manner. Notably, the aryne atropisomers herein have allowed the practical syntheses of a small nanographene as well as some triptycene and anthracene derivatives that embed stereogenic axes of controlled absolute configurations.
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Aryne Atropisomers: Chiral Arynes for the Enantiospecific Synthesis of Atropisomers and Nanographene Atropisomers.
Acc Chem Res
January 2023
Aix Marseille Univ, CNRS, Centrale Marseille, ISM2, 13397 Marseille, France.
Article Synopsis
- The article discusses arynes and their application in synthetic organic chemistry, introducing the concept of atropisomerism as a time-dependent form of isomerism and chirality.
- It differentiates between racemization (a fast irreversible process) and enantiomerization (a slow reversible process), highlighting that racemization is quicker than enantiomerization.
- The findings reveal that certain aryne atropisomers can be synthesized in solution, demonstrating their potential for enantiospecific reactions, particularly with furan, and showcasing examples of their use in forming distinctive atropisomers.
Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution.
J Org Chem
August 2022
Aix Marseille Univ, CNRS, Centrale Marseille, ISM2, Marseille, France.
Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization ( 36 kJ·mol), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above -20 °C.
View Article and Find Full Text PDFEnantiospecific Syntheses of Congested Atropisomers through Chiral Bis(aryne) Synthetic Equivalents.
Chemistry
December 2022
Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France.
The synthetic equivalents of the enantiopure binaphthyl bis(aryne) atropisomers derived from BINOL (1,1'-bi-2,2'-naphtol) featuring a stereogenic axis vicinal to the two reactive triple bonds can be generated for the first time in solution in an enantiospecific manner. Using a two-step sequence based on the bidirectional [4+2] cycloaddition of furan derivatives followed by an aromatizative deoxygenation reaction, several 9,9'-bianthracenyl-based atropisomers could be prepared enantiospecifically in high enantiomeric purity. Alternatively, bidirectional reactions with anthracene, 2-bromostyrene, and perylene as the arynophiles afforded very congested bis(benzotriptycene), bis(tetraphene) and bis(anthra[1,2,3,4-ghi]perylene) nanocarbon atropisomers in equally high enantiomeric purity.
View Article and Find Full Text PDFEnantiospecific Generation and Trapping Reactions of Aryne Atropisomers.
J Am Chem Soc
October 2020
Aix Marseille Univ, CNRS, Centrale Marseille, ISM2, 13397 Marseille, France.
Enantioenriched aryne atropisomers having a biaryl stereogenic axis vicinal to the reactive triple bond are demonstrated to exist. These reaction intermediates are easily produced in situ and can undergo the standard aryne cycloaddition chemistry in an enantiospecific manner. Notably, the aryne atropisomers herein have allowed the practical syntheses of a small nanographene as well as some triptycene and anthracene derivatives that embed stereogenic axes of controlled absolute configurations.
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