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Synthesis of ( R )‐BINOL‐Derived (Cyclopentadienone)iron Complexes and Their Application in the Catalytic Asymmetric Hydrogenation of Ketones
Author(s) -
Gajewski Piotr,
RenomCarrasco Marc,
Facchini Sofia Vailati,
Pignataro Luca,
Lefort Laurent,
de Vries Johannes G.,
Ferraccioli Raffaella,
Piarulli Umberto,
Gennari Cesare
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500796
Subject(s) - chemistry , catalysis , trimethylsilyl , asymmetric hydrogenation , stereochemistry , ring (chemistry) , ketone , medicinal chemistry , residue (chemistry) , enantioselective synthesis , organic chemistry
A family of chiral (cyclopentadienone)iron complexes, featuring an ( R )‐BINOL‐derived backbone, and their application in the asymmetric hydrogenation of ketones are described. The complexes differ from each other in the substituents at the 3,3′‐positions of the binaphthyl residue (H, OH, OR, OCOR, OSO 2 R) or at the 2,5‐positions of the cyclopentadienone ring [trimethylsilyl (TMS) or Ph]. Remarkably, eight precatalysts with different 3,3′‐binaphthyl substitution [( R )‐ 1c – 1j ] were synthesized from a common parent complex [( R )‐ 1b ] through direct functional group interconversion reactions of the complexes. The 3,3′‐(bis)methoxy‐substituted precatalyst ( R )‐ 1b gave the best catalytic performance, and its application scope was assessed in the hydrogenation of several ketones. The observed ee values (up to 77 %) are much higher than those previously reported for other chiral (cyclopentadienone)iron complexes.