New Generation of Highly Reactive Allylborating Agents For Cu(I)-Catalyzed Allylation of Chiral Sulfinylimines

New Generation of Highly Reactive Allylborating Agents For Cu(I)-Catalyzed Allylation of Chiral Sulfinylimines Full article

Journal

Organic & Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539

Output data

Year: 2024, Volume: 22, Number: 23, Pages: 4680-4696 Pages count : 17 DOI: 10.1039/d4ob00291a

Authors

Alexeev Michael S. ^1,2 , Strelkova Tatiana V. ¹ , Ilyin Michael M. ¹ , Nelyubina Yulia V. ¹ , Bespalov Ivan A. ^3,4 , Medvedev Michael G. ^1,4 , Khrustalev Victor N. ^4,5 , Kuznetsov Nikolai Yu. ^1,2

Affiliations

1	A.N. Nesmeyanov Institute of Organoelement compounds, Russian Academy of Sciences, Vavilov st. 28, 119991 Moscow, Russian Federation
2	A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky Prospect 29, 119991 Moscow, Russian Federation
3	Lomonosov Moscow State University, Leninskie Gory 1 (3), Moscow, 119991, Russian Federation
4	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 29, 119991 Moscow, Russian Federation
5	Peoples Friendship University of Russia, Miklukho-Maklay st. 6, 117198 Moscow, Russian Federation

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.

Alexeev M.S. , Strelkova T.V. , Ilyin M.M. , Nelyubina Y.V. , Bespalov I.A. , Medvedev M.G. , Khrustalev V.N. , Kuznetsov N.Y.
New Generation of Highly Reactive Allylborating Agents For Cu(I)-Catalyzed Allylation of Chiral Sulfinylimines
Organic & Biomolecular Chemistry. 2024. V.22. N23. P.4680-4696. DOI: 10.1039/d4ob00291a WOS Scopus OpenAlex

≡ Web of science:	WOS:001215783200001
≡ Scopus:	2-s2.0-85192760292
≡ OpenAlex:	W4394997315