Supplementary material
Chemoselective Transfer Hydrogenation of Aldehydes and Ketones with
a Heterogeneous Iridium Catalyst in Water
Zhi Wang, Lei Huang, Longfei Geng, Rizhi Chen, Weihong Xing, Yong Wang and Jun
Huang*
* State Key Laboratory of Materials-Oriented Chemical Engineering College of Chemistry and
Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 210009 (P. R. China)
E-mail: junhuang@njtech.edu.cn
Experimental section
General Methods and Reagents
Reagents were purchased from Aladdin Reagent Company, Sigma-Aldrich Company and
Alfa-Aesar Company, and used without further purification. The GC (Shimadzu GC-2014C)
analysis was carried out with capillary column RTX-5(Cat. #10254) (RESTEK Corp. ). The size
and morphology of the nanoparticles were observed by a JEOL-2010 HRTEM operating with 200
kV. Ir content of the catalysts were measured by inductively coupled plasma (ICP) on Optima
2000DV. Thermogravimetry (TG) analysis was carried out with a STA409 instrument under dry
nitrogen at a heating rate of 20 oC/min.
The optimization of the reaction conditions
Table 1S. Ir@CN catalyzed transfer hydrogenation of 4-methyl benzaldehydea
0.5 mol% Ir@CN
HCOOH
O
OH
Entry
HCOOH
(eq)
NaOH
(eq)
Conv. (%)
Sel. (%)
pH value b
1
2
3
4
5
6
7
8
9
5
4
3.5
3
2
1.5
3.5
3.5
3.5
0
0
0
0
0
0
1
2
3
96
95
95
90
84
73
95
94
75
79
84
87
89
92
97
94
>99
>99
2.01
2.15
2.22
2.30
2.41
2.52
3.15
3.66
4.42
Supplementary material
10
a Reaction
3.5
3.5
30
>99
6.9
conditions: 4-methyl benzaldehyde, 1 mmol, water 3.5 mL, catalyst Ir@CN (48 mg, 0.5% Ir), 100 oC,
16 h; conversion and selectivity were determined by GC analysis; b the pH value were the starting pH value.
The transfer hydrogenation of 4-methyl benzaldehyde was chosen as a template reaction to
optimize reaction conditions. The amounts of formic acid and NaOH were optimized as table 1S,
and 3.5 equivalent HCOOH with 2.0 equivalent NaOH was used as the suitable reductive.
The reaction time, reaction temperature, the amount of catalyst were also optimized for the
thansfer hydrogenation of 4-methyl benzaldehyde, and the results are summarized in Table 2S.
And the continuous measurements of conversion and selectivity as a function of reaction time
were presented in Fig. 1S.
Table 2S. Ir@CN catalyzed transfer hydrogenation 4-methyl benzaldehyde under various
conditionsa
3.5 eq HCOOH 3.5 ml water
2 eq NaOH
OH
O
a Reaction
Entry
Catalyst (Ir%)
T (℃)
Time (h)
Yield (%)
1
2
3
4
5
6
7
0.5
0.5
0.5
0.5
0.5
0.25
0.1
100
100
100
60
80
100
100
16
18
20
18
18
18
18
94
99
99
67
88
68
39
conditions: 4-methyl benzaldehyde, 1 mmol; water, 3.5 mL; HCOOH, 3.5 eq.; NaOH 2.0 eq.; catalyst
Ir@CN. conversion and yield were determined by GC analysis.
Supplementary material
Fig. 1S Continuous measurements of conversion and selectivity as a function of reaction time