Amine adducts of triallylborane as highly reactive allylborating agents for Cu()-catalyzed allylation of chiral sulfinylimines

The implementation of selective catalytic processes with highly active reagents is an attractive strategy that meets the modern principles of sustainable development of chemistry. In the current study, we for the first time describe the method and general principles of Cu( i )-catalyzed allylation o...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2024, Vol.22 (23), p.468-4696
Main Authors: Alexeev, Michael S, Strelkova, Tatiana V, Ilyin, Michael M, Nelyubina, Yulia V, Bespalov, Ivan A, Medvedev, Michael G, Khrustalev, Victor N, Kuznetsov, Nikolai Yu
Format: Article
Language:English
Subjects:
Adducts
Allyl compounds
Atom economy
Catalysis
Chemical reactions
Copper
Imines
Principles
Reagents
Stereoselectivity
Substrates
Sustainable development
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Summary:The implementation of selective catalytic processes with highly active reagents is an attractive strategy that meets the modern principles of sustainable development of chemistry. In the current study, we for the first time describe the method and general principles of Cu( i )-catalyzed allylation of imines with amine adducts of allylic triorganoboranes. Triallylborane is an extremely reactive compound and cannot be used for the catalytic allylation of imines, whereas its amine adducts are ideal substrates for catalysis. The structure of the amine fragment successfully balances the safety, selectivity and stability of the allylboron reagent, allowing it to demonstrate high activity in catalytic allylation reactions, exceeding many times any known allylboranes. The obtained results are supported by quantitative kinetics data and DFT calculations. The catalytic efficacy of the system was demonstrated on model sulfinylimines (23 examples). High diastereoselectivity up to >99% was achieved, including for the gram-scale synthesis of 2-hydroxyphenyl-derivatives. Taking into account the high reactivity and unsurpassed atom-economy of amine adducts of triallylborane (AAT), they can be considered as prospective allylation reagents with Cu( i ) and other appropriate metallocatalysts. Convenient, atom-efficient allylation reagents with high selectivity and tunable reactivity, applicable to scale-up synthesis of homoallylamines.
ISSN:1477-0520
1477-0539
DOI:10.1039/d4ob00291a