Morris et al.
reported the synthesis and applications to ketone reduction of a
new series of Ru(II) catalysts in which the homochiral ligand
is linked to the η6-arene ring.16 Representative examples are
complexes 4 and 5, which can either be isolated before use or
(more conveniently) formed in situ by the treatment of dimers
6 and 7, respectively, during the reduction of ketones in formic
acid/triethylamine media. These complexes benefit from in-
creased stability due to the “three point” attachment of the ligand
to metal and also practical simplicity through the requirement
for a single reagent in the reaction. A further benefit is the well-
defined structures of the catalysts, which provide a basis for
predictable modification toward particular substrate applications.
In our most recent studies, we discovered that the “tethered”
catalyst based on monotosylated diamines, such as 1,2-diphen-
ylethanediamine (DPEN), could be significantly improved by
attaching the linking group from the “basic” amine rather than
the sulfonyl group, i.e., as in 8.16a Complex 8, which we refer
to as “reverse-tethered”, can be prepared and isolated prior to
oxazolines,8 diamines,9 phosphine oxides,10 amino acid deriva-
tives,11 tetradentate Salen-type ligands,12 and derivatives of
BINOL based phosphonites.13 We ourselves contributed to this
field through the introduction of cis-aminoindanol 3 as a ligand
and also extension of the range of applications.15 Recently, we
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