Highly regioselective and diastereodivergent aminomethylative annulation of dienyl alcohols enabled by a hydrogen-bonding assisting effect

A ligand-controlled palladium-catalyzed highly regioselective and diastereodivergent aminomethylative annulation of dienyl alcohols with aminals has been established, which allows for producing either cis - or trans -disubstituted isochromans in good yields with complete regioselectivity and good to...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2022-02, Vol.13 (8), p.2317-2323
Main Authors: Huang, Yao, Zou, Suchen, Yu, Bangkui, Yan, Xuyang, Liu, Song, Huang, Hanmin
Format: Article
Language:English
Subjects:
Alcohols
Chemical reactions
Chemistry
Dienes
Hydrogen bonding
Hydroxyl groups
Ligands
Organic chemistry
Palladium
Regioselectivity
Stereoselectivity
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Summary:A ligand-controlled palladium-catalyzed highly regioselective and diastereodivergent aminomethylative annulation of dienyl alcohols with aminals has been established, which allows for producing either cis - or trans -disubstituted isochromans in good yields with complete regioselectivity and good to excellent diastereoselectivity. Moreover, the chiral cis -products were also obtained in good yields with up to 94% ee by using a chiral phosphinamide as the ligand. Mechanistic studies revealed that the hydroxyl group plays a key role in facilitating the Pd-catalyzed Heck insertion regioselectively taking place across the internal C&z.dbd;C bond of conjugated dienes. An efficient hydrogen-bonding assisted directing strategy has been identified, which enables the Pd-catalyzed highly regioselective and diastereodivergent 3,4-difunctionalized aminomethylative annulation of dienyl alcohols with aminals.
ISSN:2041-6520
2041-6539
DOI:10.1039/d1sc06479g