2180
J. Liu et al. / Journal of Organometallic Chemistry 693 (2008) 2177–2180
added. After the biphasic mixture was stirred for 90 min, the mix-
ture was diluted with water. The aqueous layer was separated and
the organic layer was extracted with water. The combined aqueous
layers were washed with dichloromethane and the neutralized
with aqueous potassium hydroxide until pH > 10. Dichlorometh-
ane (3 ꢁ 50 ml) was added to extract the crude product. The com-
bined organic extracts were dried with sodium sulfate. The solvent
was removed by rotary evaporator to give the product as yellowish
oil. Yield: 94%. 1H NMR (CDCl3, 300 MHz) d: 6.94 (s, 4H), 6.86 (s,
2H), 4.07 (s, 2H), 2.30 (s, 2H), 1.61 (s, 4H); 13C NMR (CDCl3,
75 MHz) d: 143.0, 137.4, 128.3, 124.4, 61.0, 21.3; ESI-MS: m/z
269.1 (M++H).
4.8. General procedure for asymmetric transfer hydrogenation of
ketones in water
A suspension of 3.1 mg (0.005 mmol) of [RuCl2(p-cymene)]2 and
16 mg (0.012 mmol) of (1S,2S)-3,30,5,50-TMTsDPEN in 2 ml of H2O
was purged with argon and stirred at 40 °C for 1 h. After that
340 mg (5.0 mmol) of HCOONa and a ketone (1 mmol) were intro-
duced. The mixture was purged with argon and stirred at room
temperature. After the reaction completed, the organic compounds
were extracted with 5 ml of n-hexane. The conversion and the
enantioselectivity were determined by GC and chiral HPLC,
respectively.
4.6. Resolution of ( )-1,2-bis(3,5-dimethylphenyl)ethane-1,2-diamine
Acknowledgement
Formation of a salt with L-(+)-tartaric acid in methanol/water
and crystallization from methanol gave (S,S)-1,2-bis(3,5-dimethyl-
phenyl)ethane-1,2-diamine in 95% ee. The optical purity can be in-
creased to >99% with second crystallization. The optical purity was
determined on OD-H column after converting the diamine to its
tosylamide by reaction with 2 equiv. of toluene-4-sulfonyl chloride
in presence of triethylamine. (Hex/IPA = 90/10; 254 nm;
tminor = 8.35 min, tmajor = 18.24 min).
We thank the National Science Foundation of China (20472116)
and the Guangzhou Science Foundation for financial support of this
study. We also thank Prof. Haibin Luo for technical support of the
computational calculation.
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