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Green Chemistry
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ARTICLE
Journal Name
2008, 10, 1243. (c) K. Mori, T. Itakura and T. Akiyama, Angew.
By means the isomeric form 6’, this intermediate incorporates
to enal to provide intermediate 7 via acid-catalyzed Michael
addition. Subsequently, a cascade Michael addition of the active
methylene in 7 to the other propiolate molecule gives rise to
intermediate 8. In the presence of acid, the cyclization forming
a new C-C bond by the nucleophilic attack of the active C-H bond
in the isomeric species 8’ to provide cyclohexadiene
intermediate 9 and releases dimethyl amine.17 The easy and fast
aromatisation of 9 under the aerobic atmosphere then yields
the biaryl products. Since AcOH was used as the reaction
medium and acid catalyst, dimethylamine may get deactivated
in the acidic atmosphere by forming ammonium, explaining why
stoichiometric HNMe2 is required.
In conclusion, by means of enamine-based benzannulation, we
have developed a rather facile and simple method for the
synthesis of biaryl aldehydes and atropisomeric biaryl
aldehydes. The totally metal-free conditions, stable and simple
starting materials, free of formyl protection and deprotection,
as well as the independence to oxidant additive constitute the
unique advantage of the present method, making it a promising
new option for the research and application of biaryl aldehydes.
Chem. Int. Ed., 2016, 55, 11642.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
The work is financially supported by National Natural Science
Foundation of China (21861019) and Natural Science
Foundation of Jiangxi Province (20202ACBL203006).
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16 CCDC 2022967 contains the crystallographic data for
compound 3p reported in this paper.
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4 | J. Name., 2012, 00, 1-3
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