ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 7, pp. 1207−1218. © Pleiades Publishing, Ltd., 2015.
-Bonded Ru-TsDPEN for Catalytic Resolution
of 1,2-Propanediol by Two Transfer Hydrogenation
Chuan-Jun Yue, Li-Ping Gu, Ya-Feng Zhuang, and Bao-Liang Liu
Department of Chemical Engineering, School of Science, Changzhou Institute of Technology, Changzhou, 213022 China
Received July 15, 2015
Abstract—A new strategy was introduced for the catalytic resolution of 1,2-propanediol involving the successive
oxidative kinetic resolution and asymmetric hydrogenation by two hydrogen transfer reactions catalyzed by nano
-bonded Ru-TsDPEN [TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylene diamine]-derived catalysts
composed of two opposite conﬁ gurations. The catalysts were characterized by X-ray diffraction (XRD), trans-
mission electron microscopy (TEM), Brunauer–Emmett–Teller (BET), Fourier-transform infrared spectroscopy
(FT-IR), thermogravimetry-derivative thermogravimetry (TG-DTG) analysis, and inductively coupled plasma
atomic emission spectrometry (ICP-AES). Results showed that Ru-TsDPEN derived catalysts were successfully
grafted on the nano SiO
, affording high catalytic conversions of >99 and 99%, selectivities of 47 and 98% and
maximum ee values of >99 and >99% in the two reactions, which were due to the nano SiO
in the reaction system with high dispersion. Additionally, the catalysts exhibited excellent durability and were
ﬁ ltered and reused at least ﬁ ve times without noticeable catalysts deactivations.
The text was submitted by the authors in English.
Optically active 1,2-diols are important for preparing
various materials, such as chiral medicines and natural
products [1, 2]. Enantiomerically pure (R)-1,2-
propanediol is of critical importance to the total synthesis
of the anti-HIV pharmaceutical Tenofovir and related
functional target molecules . This class of compounds
has so far been prepared using different raw materials
including catalytic asymmetric dihydroxylation of
oleﬁ ns , Baker’s yeast reduction of phenacyl alcohol
, enzymatic hydrolysis of diol monoacetates ,
asymmetric hydrogenation (AH) of α-hydroxyl ketones
, and catalytic resolution of racemic 1,2-diols
consisting of kinetic [8, 9] or dynamic kinetic resolution
. Catalytic resolution can be improved through
efﬁ cient catalysis and green 1,2-propanediol resource
from the industrial hydrogenolysis of large and cheap
glycerol. Glycerol is a byproduct of biodiesel production
through the transesteriﬁ cation of biomass, and accounts
for approximately 10 wt % of the converted products
[11–13]. However, few studies have been conducted on
the subject. Shuklov et al.  reported that the dynamic
kinetic resolution of rac-1-tert- butoxypropan-2-ol with
isopropenyl acetate in the presence of Novozyme 435
and a ruthenium (Ru) catalyst produces enantiomerically
pure (R)-1-tert-butoxy-2-acetoxy-propane, which can
be transformed into (R)-1,2-propanediol. Iwasaki et al.
 developed the catalytic kinetic resolution method
using a chiral organotin catalyst with benzoyl chloride.
However, controversies surround the described catalytic
resolution, which involves the coordination of the
catalysts for the racemation and the resolution in one
pot for dynamic kinetic resolution, and an intrinsic of
only 50% of a desired enantiomer for kinetic resolution.
Improving these methods is an urgent issue.
The AH of acetol to chiral 1,2-propanediol has been
successfully performed in recent years by employing
various homogeneous Ru and iridium catalysts with
appropriate ligands [15–17]. Meanwhile, asymmetric