In this Communication, we report an unprecedented β‐regioselective radical inverse hydroboration (compared with ionic hydroboration) of α,β‐unsaturated amides with NHC‐BH3 enabled by photoredox catalysis. Density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the β‐regioselective radical hydroboration, by lowering the energy barrier in comparison with other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse β‐borylated amides in synthetically useful yields under mild conditions.
A B(C6F5)3‐catalyzed hydroarylation of a series of 1,3‐dienes with various phenols has been established through a combination of theoretical and experimental investigations, affording structurally diverse ortho‐allyl phenols. DFT calculations show that the reaction proceeds through a borane‐promoted protonation/Friedel–Crafts pathway involving a π‐complex of a carbocation–anion contact ion pair. This protocol features simple and mild reaction conditions, broad functional‐group tolerance, and low catalyst loading. The obtained ortho‐allyl phenols could be further converted into flavan derivatives using B(C6F5)3 with good cis diastereoselectivity. Furthermore, this transformation was applied in the late‐stage modification of pharmaceutical compounds.
A practical and efficient
Lewis acid-catalyzed radical–radical
coupling reaction of N-hydroxyphthalimide esters
and 4-cyanopyridines with inexpensive bis(pinacolato)diboron as reductant
has been developed. With ZnCl2 as the catalyst, a wide
range of quaternary 4-substituted pyridines, including highly congested
diarylmethyl and triarylmethyl substituents, could be selectively
obtained in moderate to good yields with broad functional group tolerance.
Combined theoretical calculations and experimental studies indicate
that the Lewis acid could coordinate with the cyano group of the pyridine-boryl
radical to lower the activation barrier of the C–C coupling
pathway, leading to the formation of 4-substituted pyridines. Moreover,
it could also facilitate the decyanation/aromatization of the radical–radical
coupling intermediate.
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