Copper(I)-catalyzed asymmetric 1,6-conjugate allylation

Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimet...

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Bibliographic Details
Published in:Nature communications 2020-10, Vol.11 (1), p.5480-5480, Article 5480
Main Authors: Shi, Chang-Yun, Pan, Zhi-Zhou, Tian, Ping, Yin, Liang
Format: Article
Language:English
Subjects:
140/131
140/58
639/638/403/933
639/638/77/883
639/638/77/888
Allyl compounds
Aromatic compounds
Asymmetry
Carbonyl compounds
Carbonyls
Chemical reactions
Conjugates
Coordination compounds
Copper
Dioxins
Enantiomers
Humanities and Social Sciences
Hydroxyl groups
multidisciplinary
Phenolic compounds
Phenols
Reagents
Science
Science (multidisciplinary)
Substitutes
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Summary:Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4 H -1,3-dioxin-4-ones. The phenolic hydroxyl group in NHC ligands is found to be pivotal to obtain the desired products. Both aryl group and alkyl group at δ-position are well tolerated with the corresponding products generated in moderate to high yields and high enantioselectivity. Moreover, both 2-substituted and 3-substituted allylboronates serve as acceptable allylation reagents. At last, the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups. Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve due to competing 1,2-addition. Here, the authors report a copper(I)-catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones with good scope and high enantioselectivity.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-020-19293-9