Cationic Iridium/Chiral Bisphosphine‐Catalyzed Enantioselective Hydroacylation of Ketones

A facile and convenient synthesis of the chiral phthalide framework catalyzed by cationic iridium was developed. The method utilized cationic iridium/bisphosphine‐catalyzed asymmetric intramolecular carbonyl hydroacylation of 2‐keto benzaldehydes to furnish the corresponding optically active phthali...

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Bibliographic Details
Published in:Chemistry, an Asian journal an Asian journal, 2020-06, Vol.15 (12), p.1858-1862
Main Authors: Shirai, Tomohiko, Iwasaki, Tomoya, Kanemoto, Kazuya, Yamamoto, Yasunori
Format: Article
Language:English
Subjects:
Carbonyls
cationic iridium
Cations
Chemical synthesis
Chemistry
C−H activation
Deuteration
Deuterium
Enantiomers
enantioselective
hydroacylation
Iridium
Isotope effect
ketone
Ketones
Optical activity
Substrates
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Summary:A facile and convenient synthesis of the chiral phthalide framework catalyzed by cationic iridium was developed. The method utilized cationic iridium/bisphosphine‐catalyzed asymmetric intramolecular carbonyl hydroacylation of 2‐keto benzaldehydes to furnish the corresponding optically active phthalide products in good to excellent enantioselectivities (up to 98% ee). The mechanistic studies using a deuterium‐labelled substrate suggested that the reaction involved an intramolecular carbonyl insertion mechanism to iridium hydride intermediate. In addition, we investigated the kinetic isotope effect (KIE) of intramolecular hydroacylation with deuterated substrate and determined that the C−H activation step is not included in the turnover‐limiting step. A facile and convenient synthesis of a chiral phthalide framework catalyzed by cationic iridium was developed. The method utilized cationic iridium/bisphosphine‐catalyzed asymmetric intramolecular carbonyl hydroacylation of 2‐keto benzaldehydes to furnish the corresponding optically active phthalide products in good to excellent enantioselectivities (up to 98% ee).
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.202000386