Chain Walking of Allylrhodium Species Towards Esters During Rhodium‐Catalyzed Nucleophilic Allylations of Imines
نویسندگان
چکیده
Allylrhodium species derived from δ-trifluoroboryl β,γ-unsaturated esters undergo chain walking towards the ester moiety. The resulting allylrhodium species react with imines to give products containing two new stereocenters and a Z-alkene. By using a chiral diene ligand, products can be obtained with high enantioselectivities, where a pronounced matched/mismatched effect with the chirality of the allyltrifluoroborate is evident.
منابع مشابه
The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines**
Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes.
متن کاملEnantioselective Rhodium‐Catalyzed Coupling of Arylboronic Acids, 1,3‐Enynes, and Imines by Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration
A chiral rhodium complex catalyzes the highly enantioselective coupling of arylboronic acids, 1,3-enynes, and imines to give homoallylic sulfamates. The key step is the generation of allylrhodium(I) species by alkenyl-to-allyl 1,4-rhodium(I) migration.
متن کاملPartridge, Benjamin M. and Callingham, Michael and Lewis, William and Lam, Hon Wai (2017) Arylative intramolecular allylation of ketones with 1,3-enynes enabled by catalytic alkenyl-to-allyl 1,4-Rh(I) migration
Alkenyl-to-allyl 1,4-rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C@H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1,3-enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantiosel...
متن کاملOne-pot preparation of chiral beta-amino esters by rhodium-catalyzed three-components coupling reaction.
Chiral beta-amino esters are synthesized in one-pot from three components, amines, aldehydes, and ethyl bromoacetate, under the rhodium-catalyzed Reformatsky-type reaction condition, where complete diastereoselection is achieved in the nucleophilic addition step of ethyl bromoacetate to the imines prepared in
متن کاملDesymmetrizations of meso-tert-norbornenols by rhodium(I)-catalyzed enantioselective retro-allylations.
Rhodium-catalyzed desymmetrizations of meso-tert-norbornenols by retro-allylations generate allyl-rhodium species that allow for a rich and diverse downstream reactivity.
متن کامل