Calcium catalyzed enantioselective intramolecular alkene hydroamination with chiral C2-symmetric bis-amide ligands.
Dalton Trans
; 50(9): 3178-3185, 2021 Mar 09.
Article
em En
| MEDLINE
| ID: mdl-33594995
ABSTRACT
The chiral building block (R)-(+)-2,2'-diamino-1,1'-binaphthyl, (R)-BINAM, which is often used as backbone in privileged enantioselective catalysts, was converted to a series of N-substituted proligands R1-H2 (R = CH2tBu, C(H)Ph2, PPh2, dibenzosuberane, 8-quinoline). After double deprotonation with strong Mg or Ca bases, a series of alkaline earth (Ae) metal catalysts R1-Ae·(THF)n was obtained. Crystal structures of these C2-symmetric catalysts have been analyzed by quadrant models which show that the ligands with C(H)Ph2, dibenzosuberane and 8-quinoline substituents should give the best steric discrimination for the enantioselective intramolecular alkene hydroamination (IAH) of the aminoalkenes H2C[double bond, length as m-dash]CHCH2CR'2CH2NH2 (CR'2 = CPh2, CCy or CMe2). The dianionic R12- ligand in R1-Ae·(THF)n functions as reagent that deprotonates the aminoalkene substrate, while the monoanionic (R1-H)- ligand formed in this reaction functions as a chiral spectator ligand that controls the enantioselectivity of the ring closure reaction. Depending on the substituent R in the BINAM ligand, full cyclization of aminoalkenes to chiral pyrrolidine products as fast as 5 minutes was observed. Product analysis furnished enantioselectivities up to 57% ee, which marks the highest enantioselectivity reported for Ca catalyzed IAH. Higher selectivities are impeded by double protonation of the R12- ligand leading to complete loss of chiral information in the catalytically active species.
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Bases de dados:
MEDLINE
Idioma:
En
Revista:
Dalton Trans
Assunto da revista:
QUIMICA
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
Alemanha