Regioselective and diastereodivergent organocatalytic asymmetric vinylogous Michael addition

Regioselective and diastereodivergent asymmetric vinylogous Michael addition (AVMA) between β-substituted-cyclohexenones and nitroalkenes via dienamine activation under complementary chiral aminocatalysts was reported. γ-Regioselective AVMA of β-alkyl-cyclohex-2-enones via a linear exo-dienamine mec...

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Bibliographic Details
Published in:Organic chemistry frontiers an international journal of organic chemistry 2021-09, Vol.8 (17), p.4758-4766
Main Authors: Zou, Chuncheng, Lv, Yanting, Lu, Min, Li, Xin, Zhang, Lei, Yang, Lei, Liu, Zhen, Yanxiong Ke, Song, Gonghua, Ye, Jinxing
Format: Article
Language:English
Subjects:
Adducts
Asymmetry
Crystallography
Hydrogen bonding
Ketones
Organic chemistry
Regioselectivity
Stereoselectivity
Steric hindrance
Substitutes
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Summary:Regioselective and diastereodivergent asymmetric vinylogous Michael addition (AVMA) between β-substituted-cyclohexenones and nitroalkenes via dienamine activation under complementary chiral aminocatalysts was reported. γ-Regioselective AVMA of β-alkyl-cyclohex-2-enones via a linear exo-dienamine mechanism and γ′-regioselective functionalization of β-substituted-cyclohex-3-enones via a cyclic extended endo-dienamine mechanism were reported in satisfactory yields with high enantio- and diastereoselectivities. DFT calculations reasonably explained that the diastereoselectivity of the reactions at the γ- and γ′-positions is achieved by regulating the orientation of the nitroalkenes through the hydrogen-bonding interaction and steric hindrance effect. Furthermore, the four different configurations of the γ- and γ′-adducts were diversified to the corresponding enantioenriched spirocyclic ketones and cis-2-decalones with multiple chiral centers.
ISSN:2052-4110
2052-4110
DOI:10.1039/d1qo00371b