Different chiral diphosphine ligands were successfully applied to the rhodium catalyzed asymmetric conjugate addition of differently substituted boronic acids to 3-azaarylpropenones containing both pyridinyl and imidazolyl cores. Atropoisomeric (S)-TetraMe-BITIANP (L1) and (S)-BITIANP (L2), together with ligands bearing a mixed chirality as (S,S,Sax)-DIOPHEP (L3), (R,Rax)-ISAPHOS C1 (L4) and (S,Rax,Rax)-ISAPHOS C2 (L5), and the ones containing a stereogenic sp3 carbon ((R,R)-ZEDPHOS L6, (R,R)-EPHOS L8 and their derivatives L7 and L9) have been employed as source of chirality in rhodium complexes. Among this last class of diphosphines, the new phosphorus-based ligand called (R,R)-EPHOS (L8) has been synthesized and employed for the first time as a chiral ligand in rhodium complex for its catalytic activity. Computational studies suggested a cis coordination with a wide bite angle. When applied to the asymmetric conjugate addition of phenyl boronic acid to 3-azaarylpropenone 1, the catalytic system bearing L8 afforded the product 1a in a remarkable 94% e.e. in THF.

New sp3 diphosphine-based rhodium catalysts for the asymmetric conjugate addition of aryl boronic acids to 3-azaarylpropenones / G. Facchetti, M. Fusè, T. Pecoraro, D. Nava, I. Rimoldi. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1144-0546. - (2021), pp. 1-7. [Epub ahead of print] [10.1039/D1NJ03634C]

New sp3 diphosphine-based rhodium catalysts for the asymmetric conjugate addition of aryl boronic acids to 3-azaarylpropenones

G. Facchetti
Primo
;
D. Nava
Penultimo
;
I. Rimoldi
Ultimo
2021

Abstract

Different chiral diphosphine ligands were successfully applied to the rhodium catalyzed asymmetric conjugate addition of differently substituted boronic acids to 3-azaarylpropenones containing both pyridinyl and imidazolyl cores. Atropoisomeric (S)-TetraMe-BITIANP (L1) and (S)-BITIANP (L2), together with ligands bearing a mixed chirality as (S,S,Sax)-DIOPHEP (L3), (R,Rax)-ISAPHOS C1 (L4) and (S,Rax,Rax)-ISAPHOS C2 (L5), and the ones containing a stereogenic sp3 carbon ((R,R)-ZEDPHOS L6, (R,R)-EPHOS L8 and their derivatives L7 and L9) have been employed as source of chirality in rhodium complexes. Among this last class of diphosphines, the new phosphorus-based ligand called (R,R)-EPHOS (L8) has been synthesized and employed for the first time as a chiral ligand in rhodium complex for its catalytic activity. Computational studies suggested a cis coordination with a wide bite angle. When applied to the asymmetric conjugate addition of phenyl boronic acid to 3-azaarylpropenone 1, the catalytic system bearing L8 afforded the product 1a in a remarkable 94% e.e. in THF.
Settore CHIM/03 - Chimica Generale e Inorganica
Settore CHIM/02 - Chimica Fisica
set-2021
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/864968
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