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Synfacts 2023; 19(08): 0813
DOI: 10.1055/s-0042-1751970
Organo- and Biocatalysis

Chiral-Phosphoric-Acid-Catalyzed Asymmetric Dearomatization of Indole Derivatives

Contributor(s):
Benjamin List
,
Marian Guillén
Huang X.-Y, Xie P.-P, Zou L.-M, Zheng C, *, You S.-L. * Shanghai Institute of Organic Chemistry and East China University of Science and Technology, Shanghai, P. R. of China
Asymmetric Dearomatization of Indoles with Azodicarboxylates via Cascade Electrophilic Amination/Aza-Prins Cyclization/Phenonium-like Rearrangement.

J. Am. Chem. Soc. 2023;
145: 11745-11753
DOI: 10.1021/jacs.3c02773.
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Key words

asymmetric dearomatization - indoles - rearrangement - azodicarboxylates

Significance

Zheng, You and co-workers report the chiral-phosphoric-acid-catalyzed synthesis of enantionenriched aza-[3.3.1]-bicyclic enamines and ketones via asymmetric dearomatization of indoles­ with azodicarboxylates. The presence or absence of water as the additive in the reaction determines whether the enamine or ketone products are obtained. In both cases, the products were obtained in moderate to excellent yields and good to excellent enantioselectivities.


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Comment

According to the control experiments and DFT calculations, reaction proceeds via an electrophilic amination (which was recognized as the enantiodetermining step) followed by an aza-Prins cyclization and a phenonium-like rearrangement. The enamine products remained intact when exposed to the catalyst and water, which suggests that ketone products are not generated via hydrolysis of the corresponding enamine products, but via an alternative pathway.


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Publication History

Article published online:
14 July 2023

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