Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol under Neutral Conditions Catalyzed by a Metal-Ligand Bifunctional Catalyst [Cp?Ir(2,2′-bpyO)(H2O)]

Article abstract of DOI:10.1021/acs.joc.7b03174

A Cp?Ir complex bearing a functional bipyridonate ligand [Cp?Ir(2,2′-bpyO)(H₂O)] was found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions. It was noteworthy that many readily reducible or labile functional groups such as nitro, cyano, ester, and halide did not undergo any change under the reaction conditions. Furthermore, this catalytic system exhibited high activity for transfer hydrogenation of ketones with isopropanol. Notably, this research exhibited new potential of metal-ligand bifunctional catalysts for transfer hydrogenation.

Full text of DOI:10.1021/acs.joc.7b03174

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Article
Transfer Hydrogenation of Aldehydes and Ketones with
Isopropanol under Neutral Conditions Catalyzed by a
Metal-Ligand Bifunctional Catalyst [Cp*Ir(2,2’-bpyO)(H2O)]
Rongzhou Wang, Yawen Tang, Meng Xu, Chong Meng, and Feng Li
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b03174 • Publication Date (Web): 13 Jan 2018
Downloaded from http://pubs.acs.org on January 15, 2018
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Transfer Hydrogenation of Aldehydes and Ketones
with Isopropanol under Neutral Conditions
Catalyzed by a Metal-Ligand Bifunctional Catalyst
[Cp*Ir(2,2’-bpyO)(H2O)]
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Rongzhou Wang, Yawen Tang, Meng Xu, Chong Meng, and Feng Li*
* E-mail: fengli@njust.edu.cn.
School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing 210094,
People’s Republic of China
R
R
OH
O
O
[Cp*Ir(2,2'-bpyO)(H2O)] (0.2 mol %)
R1
R1
OH
Ir H2O
O
O
N
R2
R2
R2
R2
iPrOH, 82 oC, 6 h
N
under neutral conditions
functional group friendly
up to 98% yield
52 examples
Metal-ligand bifunctional catalyst
R1
O
R1
OH
Abstract:
A Cp*Ir complex bearing a functional bipyridonate ligand [Cp*Ir(2,2’-bpyO)(H2O)] was
found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and
chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral
conditions. It was noteworthy that many readily reducible or labile functional groups such as
nitro, cyano, ester and halide did not undergo any change under the reaction conditions.
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Furthermore, this catalytic system exhibited highly activity for transfer hydrogenation of ketones
with isopropanol. Notably, this research exhibited new potential of metal-ligand bifunctional
catalysts for transfer hydrogenation.
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■ Introduction
The reduction of aldehydes to primary alcohols represents one of the most fundamental
reactions in organic synthesis both on laboratory and industry scale.1 Traditionally, such
transformations were performed in the presence the use of stoichiometric amount of metal
hydrides such as NaBH4 and LiAlH4 with the generation of a large amount of side products.
Along with increasing environmental awareness, transition metal-catalyzed hydrogenation of
aldehydes with hydrogen gas2 and transfer hydrogenation with HCOOM (M = Na,3 NH4,4 H5)
have been developed in recent years. In past decades, transition metal-catalyzed transfer
hydrogenation of ketones to secondary alcohols with isopropanol as a hydrogen sourcce has
attracted much attention due to that isopropanol is inexpensive and easy available, the moderate
boiling point eases the separation from reaction products and highly efficiency.6 However, the
use of isopropanol as a hydrogen source for transfer hydrogenation of aldehydes remains less
unexplored.7 It may be attributed to that such transfer hydrogenation usually required the
presence of base for the activation of isopropanol and aldehydes are far more sensitive than
ketones, and thus self-aldol side reactions could unavoidably occurred under basic conditions.
From both synthetic and environmental points of view, the development of an efficient and
general organometallic catalyst for transfer hydrogen of aldehydes to primary alcohols with
isopropanol under neural condition is apparently highly desirable.
Recently, Fujita, Yamaguchi and co-workers reported a series of Cp*Ir complexes bearing a
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functional bipyridine or a bipyridonate ligand, which exhibited highly catalytic activity for
acceptorless dehydrogenation of alcohols and N-heterocycles based on the concept of “ligand
promoted dehydrogenation”.8 More recently, we demonstrated that such complexes are highly
effective metal-ligand bifunctional catalysts for the N-alkylation of sulfonamides with alcohols
based on hydrogen autotransfer process9 and acceptorless dehydrogenative coupling for the
construction of quinazolinones and quinolines.10 As a continuing effort to develop iridium-
catalyzed environmentally benign transformations,9-11 we herein are interested in exploring the
feasibility of transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of
unsaturated aldehydes with isopropanol under neutral conditions catalyzed by a metal-ligand
bifunctional catalyst. Furthermore, transfer hydrogenation of ketones with isopropanol was also
investigated.
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Results and Discussion
In our initial experiment, the transfer hydrogenation of benzaldehyde (1a) with isopropanol
was selected as a model reaction (Scheme 1). In the presence of [Cp*IrCl2]2 (Cp* =
pentamethylcyclopentadienyl) (cat. 1), [Cp*Ir(2-phenylpyridine-kC,N)]Cl (cat. 2),
[Cp*Ir(bpy)Cl)][Cl] (cat. 3) and [Cp*Ir(bpy)(H2O)][OTf]2 (cat. 4) (0.2 mol%), the reaction was
o
carried out for 6 h at 82 C and the product 2a was obtained in ≤ 18% yield. When a series of
Cp*Ir complexes bearing a functional bipyridine or bipyridonate ligand, such as [Cp*Ir(2-
(OH)py)]Cl2 (cat. 5), Cp*Ir[2-(2-(2-(OH)py)phenyl]Cl (cat. 6), [Cp*Ir(6,6’-(OH)2-2,2’-
bpy)(H2O)][OTf]2 (cat. 7) and [Cp*Ir(2,2’-bpyO)(H2O)] (cat. 8), were screened and yields of 2a
were obviously enhanced. Apparently, the presence of functional units in the ligand is crucially
important for the activity of catalysts. Among them, cat. 8 exhibited the highest activity and the
product 2a was obtained in > 98% yield.12 Using rhodium analogs [Cp*Rh(2,2’-bpyO)(H2O)]
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Scheme 1. Transfer Hydrogenation of Benzaldehyde with Isopropanol using a Range of
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Catalysts.a,b
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8
9
catalyst (0.2 mol %)
OH
O
iPrOH, 82 oC, 6 h
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1a
2a
[OTf]2
Cl-
Cl
Cl
Cl
Ir
Ir
Ir H2O
N
Ir Cl
Ir Cl
N
N
N
Cl
N
cat. 4, 10% yield
cat. 1, 18% yield
cat. 2, n.d.
cat. 3, n.d.
[OTf]2
HO
HO
HO
Ir Cl
N
Ir Cl
Cl
Ir H2O
OH
N
N
cat. 5, 25% yield
cat. 6, 35% yield
cat. 7, 90% yield
O
O
O
Ir H2O
Rh H2O
O
Ru H2O
N
O
N
N
O
N
N
N
cat. 8, > 98% yield (93%c)
cat. 9, 40% yield
cat. 10, < 5% yield
aReactions conditions: 1a (1 mmol), isopropanol (5 mL), catalyst (0.2 mol %), 82 oC, under N2,
6 h. bYield was determined based on the 1H NMR spectrum of the crude reaction. cYield.
(cat. 9) as an alternative catalysts, the product 2a was obtained in 40% yield. However, only < 5
% yield of 2a was observed when a ruthenium analogs [(p-cymene)Ru(2,2’-bpyO)(H2O)] (cat.
10) was examined.
With the identified catalyst in hand, we investigated the scope of transfer hydrogenation with a
variety of aldehydes (1) catalyzed by cat. 8, and these results are shown in Table 1. Reactions of
benzaldehyde bearing one or two electron-donating substituents, such as methyl, dimethyl,
isopropyl, hydroxyl, methoxy, dimethoxy and dimethylamino groups, afforded the desired
products 2b-2i in 93-96% yields (Table 1, entries 1-8). Furthermore, transformations of
benzaldehydes bearing a halogen atom, such as fluorine, chlorine and bromine, gave the
corresponding products 2j-2n in 92-96% yields (Table 1, entries 9-13). Strong electron-
withdrawing substituents, such as nitro, cyano, ester and trifluoromethoxy groups, were tolerated
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Table 1. Transfer Hydrogenation of a Variety of Aldehydes with Isopropanol.a
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7
cat. 8 (0.2 mol %)
R
R
OH
O
iPrOH, 82 oC, 6 h
8
1
2
9
Entry
Aldehyde
Product
Me
Yield (%)
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Me
OH
O
1
93
1b
2b
2c
Me
Me
OH
OH
OH
O
O
O
2
3
4
95
94
96
1c
1d
Me
Me
Me
Me
2d
Me
Me
Me
Me
1e
1f
2e
2f
OH
OH
O
O
O
5
94
MeO
MeO
MeO
MeO
MeO
MeO
6
7
96
93
1g
1h
2g
2h
OH
OH
HO
HO
O
O
8
9
95
96
Me
Me
N
N
Me
Me
1i
2i
OH
F
F
1j
2j
Cl
Cl
OH
OH
O
O
10
11
93
92
1k
2k
Cl
Cl
1l
2l
Br
Br
OH
OH
O
O
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13
94
96
1m
2m
Br
Br
1n
2n
NO2
NO2
OH
O
14
94
1o
2o
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Table 1. (Continued).
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Entry
15
Aldehyde
Product
Yield (%)
78
OH
O
O
NC
NC
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1p
2p
OH
16
17
93
88
MeO
MeO
O
O
1q
1r
2q
2r
OH
O
F3CO
F3CO
OH
OH
O
O
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19
95
1s
1t
2s
83b
N
N
2t
HO
OH
OH
O
O
O
20
96b
1u
2u
93b
96b
21
22
1v
2v
OH
OH
O
O
1w
2w
23
91b
1x
2x
aReactions conditions: 1 (1 mmol), isopropanol (5 mL), cat. 8 (0.2 mol%), 82 oC, under N2, 6 h.
b120 oC, 12 h.
and the desired products 2o-2r were obtained in 78-94% yields (Table 1, entries 14-17).
1-Naphthaldehyde and picolinaldehyde were proven to be suitable substrates, and
reactions gave the corresponding products 2s and 2t in 95% and 83% yields,
respectively (Table 1, entries 18-19). When m-phthalaldehyde was used, the desired
product 2u was obtained in 96% yield (Table 1, entry 20). The catalytic system was
also applied to aliphatic aldehydes, such as 3-phenylpropanal, octanal and
cyclohexanecarbaldehyde, giving the desired products 2v-2x in 91-96% yields (Table 1,
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entries 21-23).
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Encouraged by above promising results, we examined the chemoselective transfer
hydrogenation of a range of unsaturated aldehydes (3) with isopropanol (Table 2). The
transformation of cinnamaldehyde afforded cinnamylalcohol (4a) in 92% yield with complete
chemoselectivity (Table 2, entry 1). Similarly, cinnamaldehydes bearing an electron-donating
group or an electron-withdrawing group were converted to the corresponding products 4b-4e in
94-96% yields (Table 2, entries 2-5). Highly catalytic activities were also observed when
cinnamaldehydes bearing a substituent on the α-position were conducted and the desired
products 4f-4h were obtained in 93-97% yields (Table 2, entries 6-8). Furthermore, 3-(9-
anthryl)acrylaldehyde and 3-(2-furyl)acrylaldehyde were hydrogenated to give the corresponding
products 4i and 4j in 98% and 92% yields, respectively (Table 2, entries 9-10). In the case of
aliphatic α,β-unsaturated aldehydes, the desired products 4k and 4l were obtained in 80% and
91% yields, respectively (Table 2, entries 11-12). Interestingly, non-conjugated unsaturated
aldehydes, such as 3-cyclohexene-1-carboxaldehyde and 5-norbornene-2-carboxaldehyde, were
also successfully converted to the corresponding products 4m and 4n in 93% and 96% yields,
respectively (Table 2, entries 13-14). When 3,7-dimethyl-2,6-octadienal was served as a
substrate, only carbonyl group was hydrogenated and two C=C bonds remained unreacted (Table
2, entry 15).
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A plausible mechanism was proposed for the present transfer hydrogenation of aldehydes or
chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol (Scheme 2).
The initial stage of reaction involved the elimination of H2O from cat. 8 to give an unsaturated
species A bearing a 2,2’-bipyridonate ligand.8f In the step of the activation of isopropanol, the
ligand accepted a proton resulted in the generation of alkoxy iridium species B, which underwent
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Table 2. Chemoselective Transfer Hydrogenation of a Range of Unsaturated Aldehydes with
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Isopropanol.a
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9
cat. 8 (0.2 mol %)
R1
R1
OH
O
R2
R2
iPrOH, 82 oC, 6 h
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3
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Entry
1
Product
Unsaturated adehyde
O
Yield (%)
92b
OH
3a
4a
4b
Me
Me
OH
O
2
96c
3b
OMe
OMe
OH
OH
O
3
4
94b
96c
3c
4c
4d
O
Br
Br
3d
NO2
NO2
OH
O
5
95b
3e
4e
4f
OH
OH
O
93
97
6
7
3f
O
3g
4g
OH
O
96
8
3h
4h
OH
OH
O
9
98b
3i
4i
4j
O
10
11
92b
80
O
O
3j
O
OH
OH
3k
4k
O
12
13
91
93
3l
4l
OH
O
3m
4m
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Table 2. (Continued).
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Entry
14
Unsaturated adehyde
Product
Yield (%)
96b
O
OH
OH
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3n
4n
O
15
94
3o
4o
aReactions conditions: 3 (1 mmol), isopropanol (5 mL), cat. 8 (0.2 mol%), 82 oC, under N2, 6 h.
b120 oC, 12 h. c100 oC, 12 h.
ß-hydrogen elimination to give iridium hydride species C and acetone.13 Companied by the
process of ligand-promoted simultaneous transfer of the hydride on iridium and the hydroxy
proton on the bpy ligand of species C to the C=O bond of aldehydes or unsaturated aldehydes,
the desirable alcohols were released as final products and the catalytic species A were
regenerated.
To demonstrate the practical potential of this methodology, the large-scale reaction was
undertaken. The hydrogenation of 1a (20 mmol) was carried out in the presence of cat. 8 (0.05
mol %) to give the corresponding product 2a in 92% yield (Scheme 3).
Furthermore, transfer hydrogenation of glucose, which is unit of cellulose and exists an
equilibrium between its hemiacetal and aldehyde forms in water, was represented. The reaction
of 5 with isopripanol was performed at 120 °C in the presence of cat. 8 (0.2 mol %) for 12 h to
afford the desired product sorbitol 6 in 80% yield (Scheme 4).
The present catalytic system was also expanded to transfer hydrogenation of ketones with
isopripanol. As outlined in Table 3, reactions of a series of ketones (7) procced smoothly to give
the desired products 8 in high yields.
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Scheme 2. Proposed Reaction Mechanisms.
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9
O
Ir H2O
O
N
N
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cat. 8
+ H2O
-H2O
O
Ir
O
N
R
OH
OH
N
or
R1
OH
R
A
R2
R2
R1
O
O
Cp*
Cp*
Cp*
H
H
O
O
O
O
Ir
Ir
Ir
or
N
N
N
O
O
N
N
OH
N
H
H
:
C
C
B
Cp*
H
R
O
O
Ir
or
O
N
OH
N
R1
O
R2
C
: vacant site
Scheme 3. Large-Scale Hydrogenation of 1a with Isopropanol.
cat. 8 (0.05 mol %)
OH
O
iPrOH (50 mL)
120 oC, 12 h
1a (20 mmol)
2a, 92% yield
Scheme 4. Transfer Hydrogenation of Glucose with Isopropanol.
HO
OH OH
cat. 8 (0.2 mol %)
O
HO
HO
HO
OH
OH
iPrOH, 120 oC, 12 h
HO
OH OH
5
6, 80% yield
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Table 3. Transfer Hydrogenation of a Series of Ketones with Isopropanol.a
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6
7
8
9
R2
R2
cat. 8 (0.2 mol %)
iPrOH, 82 oC, 6 h
R1
O
R1
OH
7
8
Entry
1
Ketone
Product
Yield (%)
95
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13
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15
16
17
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O
O
O
O
OH
7a
7b
7c
8a
8b
8c
Me
Me
OH
OH
OH
2
3
4
95
86
96
MeO
MeO
F
F
7d
8d
O
OH
5
95
97
Cl
Br
Cl
Br
7e
7f
8e
8f
O
O
OH
OH
6
7
96
.
O2N
NC
O2N
NC
7g
7h
8g
8h
O
O
OH
OH
8
9
95
92
7i
8i
O
OH
10
11
93
82
7j
8j
O
O
OH
7k
8k
OH
12
91
HO
HO
7l
8l
aReactions conditions: 1 (1 mmol), isopropanol (5 mL), cat. 8 (0.2 mol%), 82 oC, under N2, 6 h.
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In summary, we have demonstrated that a Cp*Ir complex bearing a functional bipyridonate
ligand [Cp*Ir(2,2’-bpyO)(H2O)] is a highly efficient and general catalyst for transfer
hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes
with isopropanol under neutral conditions. It was noteworthy that many readily reducible or
labile functional groups such as nitro, cyano, ester and halide did not undergo any change under
present reaction conditions. Furthermore, this catalytic system exhibited highly activity for
transfer hydrogenation of ketones with isopropanol. Notably, this research exhibited new
potential of metal-ligand bifunctional catalysts for transfer hydrogenation.
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■ Experimental Section
Experimental Details. High-resolution mass spectra (HRMS) were obtained on a HPLC-Q-Tof
MS (Micro) spectrometer and are reported as m/z (relative intensity). Accurate masses are
reported for the molecular ion [M+H]+. Melting points were measured on a X-6 micro-melting
apparatus. 1H NMR spectra were recorded on a 500 spectrometer. Chemical shifts are reported in
delta (δ) units, parts per million (ppm) downfield from tetramethylsilane or ppm relative to the
center of the singlet at 7.26 ppm for CDCl3 and 2.50 ppm for DMSO-d6. Coupling constants J
values are reported in Hertz (Hz), and the splitting patterns were designated as follows: s, singlet;
d, doublet; t, triplet; m, multiplet; b, broad. 13C{1H} NMR spectra were recorded on a 125 MHz
spectrophotometer with broadband 1H decoupling. Chemical shifts are reported in delta (δ) units,
ppm relative to the center of the triplet at 77.0 ppm for CDCl3 and 39.5 ppm for DMSO-d6. All
reactions were run under an atmosphere of nitrogen, unless otherwise indicated. Analytical thin-
layer chromatography (TLC) was carried out using 0.2-mm commercial silica gel plates.
[Cp*IrCl2]2 (cat. 1),14 [Cp*Ir(2-phenylpyridine-kC,N)]Cl (cat. 2),15 [Cp*Ir(bpy)Cl)][Cl] (cat.
3),16 [Cp*Ir(bpy)(H2O)][OTf]2 (cat. 4),17 [Cp*Ir(2-(OH)py)]Cl2 (cat. 5),8a Cp*Ir[2-(2-(2-
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(OH)py)phenyl]Cl (cat. 6),8b [Cp*Ir(6,6-(OH)2bpy)(H2O)][OTf]2 (cat. 7),8c [Cp*Ir(2,2’-
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bpyO)(H2O)] (cat. 8),8d [Cp*Rh(2,2’-bpyO)(H2O)] (cat. 9)18 and
bpyO)(H2O)] (cat. 10)19 were synthesized according the previous reports.
[(p-cymene)Ru(2,2’-
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General procedure for transfer hydrogenation of aldehydes catalyzed by [Cp*Ir(2,2’-
bpyO)(H2O)] (Table 1). In a 25-mL Schlenk tube, aldehydes (1 mmol), isopropanol (5 mL), cat.
8 (1.1 mg, 0.2 mol %) were placed under an N2 atmosphere, and the reaction mixture was heated
at 82 oC in an oil bath for 6 h. The mixture was then cooled to ambient temperature, concentrated
in vacuo and purified by flash column chromatography (hexanes/ethyl acetate = 10/1) to afford
the corresponding products.
Phenylmethanol (2a).20 Light yellow oil; 93% yield (100 mg); 1H NMR (500 MHz, CDCl3) δ
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7.36-7.32 (m, 4H), 7.29-7.23 (m, 1H), 4.63 (d, J = 2.3 Hz, 2H), 2.40 (br s, 1H); C{1H} NMR
(125 MHz, CDCl3) δ 140.8, 128.5, 127.5, 126.9, 65.2.
o-Tolylmethanol (2b).21 Light yellow oil; 93% yield (114 mg); 1H NMR (500 MHz, CDCl3) δ
7.32-7.31 (m, 1H), 7.22-7.14 (m, 3H), 4.63 (d, J = 2.5 Hz, 2H), 2.60 (br s, 1H), 2.32 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ 138.6, 136.0, 130.2, 127.7, 127.5, 126.0, 63.3, 18.5.
m-Tolylmethanol (2c).22 Light yellow oil; 95% yield (116 mg); 1H NMR (500 MHz, CDCl3)
δ 7.25-7.24 (m, 1H), 7.19 (s, 1H), 7.16 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 7.5 Hz, 1H), 4.65 (s, 2H),
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2.36 (s, 3H), 1.73 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 140.7, 138.0, 128.3, 128.2, 127.6,
123.9, 65.0, 21.3.
(3,4-Dimethylphenyl)methanol (2d).23 Light yellow oil; 94% yield (128 mg); 1H NMR (500
MHz, CDCl3) δ 7.15-7.12 (m, 2H), 7.10 (d, J = 7.7 Hz, 1H), 4.62 (s, 2H), 2.27 (s, 3H), 2.26 (s,
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3H), 1.66 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 138.4, 136.8, 136.0, 129.8, 128.5, 124.6,
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65.2, 19.7, 19.5.
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(4-Isopropylphenyl)methanol (2e).24 Light yellow oil; 96% yield (144 mg); H NMR (500
MHz, CDCl3) δ 7.28 (d, J = 8.1 Hz, 2H), 7.22 (d, J = 8.1 Hz, 2H), 4.62 (s, 2H), 2.95-2.86 (m,
1H), 2.12 (br s, 1H), 1.25 (d, J = 7.0 Hz, 6H); 13C{1H} (125 MHz, CDCl3) δ 148.4, 138.3, 127.1,
126.6, 65.1, 33.8, 24.0.
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(4-Methoxyphenyl)methanol (2f).20 Light yellow oil; 94% yield (130 mg); H NMR (500
MHz, CDCl3) δ 7.30 (d, J = 8.6 Hz, 2H), 6.90 (d, J = 8.6 Hz, 2H), 4.61 (s, 2H), 3.81 (s, 3H), 1.70
(br s, 1H); 13C{1H} (125 MHz, CDCl3) δ 159.1, 133.1, 128.6, 113.9, 64.9, 55.2.
(3,4-Dimethoxyphenyl)methanol (2g).25 Light yellow oil; 96% yield (162 mg); H NMR
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(500 MHz, CDCl3) δ 6.93 (s, 1H), 6.90 (d, J = 8.1 Hz, 1H), 6.85 (d, J = 8.1 Hz, 1H), 4,62 (s, 2H),
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3.89 (s, 3H), 3.88 (s, 3H), 1.77 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 148.8, 148.3, 133.5,
119.2, 110.9, 110.3, 64.9, 55.7, 55.6.
4-(Hydroxymethyl)phenol (2h).26 Light yellow solid; 93% yield (115 mg); mp 118-119 C;
o
1H NMR (500 MHz, DMSO-d6) δ 9.23 (s, 1H), 7.11 (d, J = 8.3 Hz, 2H), 6.71 (d, J = 8.3 Hz, 2H),
4.94 (t, J = 5.7 Hz, 1H), 4.36 (d, J = 5.7 Hz, 2H); 13C{1H} (125 MHz, DMSO-d6) δ 156.2, 132.8,
128.1, 114.8, 62.8.
(4-(Dimethylamino)phenyl)methanol (2i).27 Light yellow oil; 95% yield (144 mg); 1H NMR
(500 MHz, CDCl3) δ 7.23 (d, J = 8.5 Hz, 2H), 6.72 (d, J = 8.5 Hz, 2H), 4.53 (s, 2H), 2.93 (s, 6H),
1.90 (br s, 1H); 13C{1H} (125 MHz, CDCl3) δ 150.3, 128.9, 128.5, 112.6, 65.2, 40.6.
(4-Fluorophenyl)methanol (2j).22 Light yellow oil; 96% yield (121 mg); 1H NMR (500 MHz,
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CDCl3) δ 7.32-7.30 (m, 2H), 7.05-7.01 (m, 2H), 4.63 (s, 2H), 2.20 (br s, 1H); C{1H} (125
MHz, CDCl3) δ 163.2 (d, JC-F = 244.1 Hz), 136.5, 128.7 (d, JC-F = 8.0 Hz), 115.4 (d, JC-F = 21.3
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(2-Chlorophenyl)methanol (2k).28 Light yellow solid; 93% yield (133 mg); mp 71-72 oC; 1H
NMR (500 MHz, CDCl3) δ 7.49 (d, J = 7.4 Hz, 1H), 7.38 (d, J = 7.7 Hz, 1H), 7.31-7.23 (m, 2H),
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4.79 (s, 2H), 2.15 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 138.1, 132.7, 129.3, 128.8, 128.7,
127.0, 62.8.
(4-Chlorophenyl)methanol (2l).20 White solid; 92% yield (131 mg); mp 69-70 C; H NMR
(500 MHz, CDCl3) δ 7.31-7.29 (m, 2H), 7.25-7.23 (m, 2H), 4.60 (d, J = 3.6 Hz, 2H), 2.37 (br s,
1H); 13C{1H} (125 MHz, CDCl3) δ 139.2, 133.3, 128.6, 128.2, 64.4.
o
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(3-Bromophenyl)methanol (2m).29 Light yellow oil; 94% yield (175 mg); H NMR (500
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MHz, CDCl3) δ 7.51 (s, 1H), 7.42 (d, J = 7.8 Hz, 1H), 7.27-7.20 (m, 2H), 4.64 (s, 2H), 2.09 (br s,
1H); 13C{1H} (125 MHz, CDCl3) δ 143.0, 130.6, 130.1, 129.8, 125.3, 122.6, 64.4.
(4-Bromophenyl)methanol (2n).20 Yellow solid; 96% yield (179 mg); mp 63-64 oC; 1H NMR
(500 MHz, CDCl3) δ 7.49 (d, J = 8.3 Hz, 2H), 7.24 (d, J = 8.3 Hz, 2H), 4.65 (s, 2H), 1.80 (br s,
1H); 13C{1H} (125 MHz, CDCl3) δ 139.7, 131.5, 128.5, 121.3, 64.4.
(2-Nitrophenyl)methanol (2o).20 Light yellow solid; 94% yield (144 mg); mp 69-70 C; H
NMR (500 MHz, CDCl3) δ 8.11 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 7.7 Hz, 1H), 7.68 (t, J = 7.5 Hz,
1H), 7.48 (t, J = 7.8 Hz, 1H), 4.98 (s, 2H), 2.60 (br s, 1H); 13C{1H} (125 MHz, CDCl3) δ 147.5,
136.8, 134.1, 129.8, 128.4, 124.9, 62.4.
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4-(Hydroxymethyl)benzonitrile (2p).20 White solid; 78% yield (104 mg); mp 41-42 C; H
NMR (500 MHz, CDCl3) δ 7.66 (d, J = 8.2 Hz, 2H), 7.49 ((d, J = 8.2 Hz, 2H), 4.79 (s, 2H), 1,91
(br s, 1H); 13C{1H} (125 MHz, CDCl3) δ 146.3, 132.2, 126.9, 118.8, 110.9, 64.0.
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Methyl 4-(hydroxymethyl)benzoate (2q).29 White solid; 93% yield (155 mg); mp 48-49 C;
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1H NMR (500 MHz, CDCl3) δ 8.04-8.0 (m, 2H), 7.45-7.41 (m, 2H), 4.78-4.75 (m, 2H), 3.92-
3.91 (m, 3H); 13C{1H} (125 MHz, CDCl3) δ 167.0, 146.1, 129.7, 129.0, 126.3, 64.4, 52.0.
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(4-(Trifluoromethoxy)phenyl)methanol (2r).30 Light yellow oil; 88% yield (169 mg); H
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NMR (500 MHz, CDCl3) δ 7.39 (d, J = 7.9 Hz, 2H), 7.21 (d, J = 8.1 Hz, 2H), 4.69 (d, J = 6.8 Hz,
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2H), 2,21 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 148.6, 139.4, 128.3, 121.5 (q, JC-F = 255.5
Hz), 121.0, 64.4.
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Naphthalen-1-ylmethanol (2s).24 Light yellow solid; 95% yield (150 mg); mp 58-59 C; H
NMR (500 MHz, CDCl3) δ 8.15 (d, J = 8.4 Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.83 (d, J = 8.2 Hz,
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1H), 7.57-7.50 (m, 3H), 7.45 (t, J = 7.6 Hz, 1H), 5.17 (s, 2H), 1.74 (br s, 1H); C{1H} (125
MHz, CDCl3) δ 136.2, 133.7, 131.1, 128.6, 128.4, 126.2, 125.8, 125.3, 125.2, 123.6, 63.4.
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Pyridin-2-ylmethanol (2t).20 Light yellow oil; 83% yield (91 mg); H NMR (500 MHz,
CDCl3) δ 8.51 (d, J = 4.8 Hz, 1H), 7.69-7.66 (td, J = 7.7 and 1.7 Hz, 1H), 7.33 (d, J = 7.8 Hz,
1H), 7.20-7.17 (m, 1H), 4.76 (s, 2H), 4.56 (br s, 1H); 13C{1H} (125 MHz, CDCl3) δ 159.6, 148.4,
136.7, 122.2, 120.7, 64.2.
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1,3-Benzenedimethanol (2u).31 Light yellow oil; 96% yield (132 mg); H NMR (500 MHz,
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CDCl3) δ 7.31-7.28 (m, 2H), 7.21 (d, J = 7.8 Hz, 2H), 4.58 (s, 4H), 2.88 (br s, 1H); C{1H}
(125 MHz, CDCl3) δ 141.1, 128.6, 126.1, 125.5, 64.8.
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3-Phenylpropan-1-ol (2v).32 Light yellow oil; 93% yield (127 mg); H NMR (500 MHz,
CDCl3) δ 7.29-7.27 (m, 2H), 7.20-7.17 (m, 3H), 3.66 (t, J = 6.5 Hz, 2H), 2.70 (t, J = 7.8 Hz, 2H),
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2.39 (br s, 1H), 1.91-1.86 (m, 2H); C{1H} (125 MHz, CDCl3) δ 141.8, 128.4, 128.3, 125.8,
62.2, 34.1, 32.0.
Octan-1-ol (2w).33 Light yellow oil; 96% yield (125 mg); 1H NMR (500 MHz, CDCl3) δ 3.64
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(t, J = 6.7 Hz, 2H), 2.45 (br s, 1H), 1.59-1.54 (m, 2H), 1.36-1.23 (m, 10H), 0.88 (t, J = 6.9 Hz,
3H); 13C{1H} (125 MHz, CDCl3) δ 63.0, 32.7, 31.8, 29.4, 29.2, 25.7, 22.6, 14.0.
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Cyclohexylmethanol (2x).34 Light yellow oil; 91% yield (104 mg); H NMR (500 MHz,
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CDCl3) δ 3.43 (d, J = 6.4 Hz, 2H), 2.08 (br s, 1H), 1.76-1.66 (m, 5H), 1.51-1.44 (m, 1H), 1.30-
1.12 (m, 3H), 0.97-0.89 (m, 2H); 13C{1H} (125 MHz, CDCl3) δ 68.6, 40.4, 29.5, 26.5, 25.8.
Procedure for chemoselective transfer hydrogenation of unsaturated aldehydes with
isopropanol catalyzed by [Cp*Ir(2,2’-bpyO)(H2O)] (Table 2). In a 25-mL Schlenk tube,
unsaturated aldehydes (1 mmol), isopropanol (5 mL), cat. 8 (1.1 mg, 0.2 mol %) were placed
under an N2 atmosphere, and the reaction mixture was heated at 82 oC in an oil bath for 6 h. The
mixture was then cooled to ambient temperature, concentrated in vacuo and purified by flash
column chromatography (hexanes/ethyl acetate = 10/1) to afford the corresponding products.
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3-Phenylprop-2-en-1-ol (4a).3b Light yellow oil; 92% yield (123 mg); H NMR (500 MHz,
CDCl3) δ 7.36 (d, J = 7.8 Hz, 2H), 7.29 (t, J = 7.6 Hz, 2H), 7.22 (t, J = 7.3 Hz, 1H), 6.59 (d, J =
16.0 Hz, 1H), 6.33 (dt, J = 15.9 and 5.7 Hz, 1H), 4.28 (d, J = 5.7 Hz, 2H), 2.34 (br s, 1H);
13C{1H} (125 MHz, CDCl3) δ 136.6, 130.9, 128.5, 128.4, 127.6, 126.4, 63.5.
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3-M-tolylprop-2-en-1-ol (4b).35 Light yellow oil; 96% yield (142 mg); H NMR (500 MHz,
CDCl3) δ 7.23-7.19 (m, 3H), 7.07 (d, J = 6.6 Hz, 1H), 6.60 (d, J = 15.9 Hz, 1H), 6.36 (dt, J =
15.9 and 5.8 Hz, 1H), 4.33 (d, J = 5.6 Hz, 2H), 2.35 (s, 3H); 13C{1H} (125 MHz, CDCl3) δ 138.1,
136.6, 131.2, 128.4, 128.3, 127.2, 123.6, 63.6, 21.3.
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3-(2-Methoxyphenyl)prop-2-en-1-ol (4c).36 Light yellow oil; 94% yield (154 mg); H NMR
(500 MHz, CDCl3) δ 7.43 (d, J = 7.6 Hz, 1H), 7.24-7.21 (m, 1H), 6.92 (t, J = 7.5 Hz, 2H), 6.87
(d, J = 8.2 Hz, 1H), 6.38 (dt, J = 16.1 and 5.9 Hz, 1H), 4.32 (d, J = 5.9 Hz, 2H), 3.84 (s, 3H),
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1.83 (br s, 1H); C{1H} (125 MHz, CDCl3) δ 156.7, 129.2, 128.7, 126.9, 126.1, 125.7, 120.6,
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110.8, 64.1, 55.4.
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3-(4-Bromophenyl)prop-2-en-1-ol (4d).37 Yellow solid; 96% yield (205 mg); mp 55-56 C;
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1H NMR (500 MHz, CDCl3) δ 7.45 (d, J = 8.5 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H), 6.57 (d, J =
16.0 Hz, 1H), 6.36 (dt, J = 15.9 and 5.6 Hz, 1H), 4.32 (dd, J J = 1.45 and 5.6 Hz, 2H), 1.63 (br s,
1H); 13C{1H} (125 MHz, CDCl3) δ 135.6, 131.7, 129.8, 129.7, 129.3, 128.0, 121.4, 63.5, 63.4.
3-(2-Nitrophenyl)prop-2-en-1-ol (4e).36 Light yellow solid; 95% yield (170 mg); mp 59-61
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oC; H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz, 1H), 7.61-7.55 (m, 2H), 7.40 (t, J = 7.6
Hz, 1H), 7.10 (d, J = 15.7 Hz, 1H), 6.35 (dt, J = 15.8 and 5.3 Hz, 1H), 4.39 (d, J = 4.9 Hz, 2H),
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124.5, 63.2.
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2-Methyl-3-phenylprop-2-en-1-ol (4f).3b Light yellow oil; 93% yield (138 mg); H NMR
(500 MHz, CDCl3) δ 7.33 (t, J = 7.6 Hz, 2H), 7.28 (d, J = 7.5 Hz, 2H), 7.24-7.20 (m, 1H), 6.52 (s,
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1H), 4.17 (s, 2H), 2.15 (br s, 1H), 1.89 (s, 3H); C{1H} (125 MHz, CDCl3) δ 137.6, 137.5,
128.8, 128.1, 126.4, 125.0, 68.9, 15.2.
2-Benzylideneheptan-1-ol (4g).3b Light yellow oil; 97% yield (197 mg); 1H NMR (500 MHz,
CDCl3) δ 7.39 (t, J = 7.6 Hz, 2H), 7.31-7.26 (m, 3H), 6.59 (s, 1H), 4.28 (s, 2H), 2.34 (t, J = 8.1
Hz, 2H), 1.86 (br s, 1H), 1.59-1.53 (m, 2H), 1.36-1.35 (m, 4H), 0.95-0.92 (t, J = 6.6 Hz, 3H);
13C{1H} (125 MHz, CDCl3) δ 142.4, 137.5, 128.6, 128.1, 126.4, 125.2, 66.9, 32.0, 28.7, 28.0,
22.4, 14.0.
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2-Benzylideneoctan-1-ol (4h).3b Light yellow oil; 96% yield (209 mg); H NMR (500 MHz,
CDCl3) δ 7.32 (t, J = 7.6 Hz, 2H), 7.25-7.20 (m, 3H), 6.52 (s, 1H), 4.22 (s, 2H), 2.29 (t, J = 8.1
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Hz, 2H), 1.56 (br s, 1H), 1.52-1.46 (m, 2H), 1.32-1.26 (m, 6H), 0.87 (t, J = 6.9 Hz, 3H); 13C{1H}
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3-(Anthracen-9-yl)prop-2-en-1-ol (4i). Light yellow solid; 98% yield (229 mg); mp 81-82 oC;
1H NMR (500 MHz, CDCl3) δ 8.35 (s, 1H), 8.27-8.25 (m, 2H), 7.97-7.95 (m, 2H), 7.44-7.42 (m,
4H), 7.37 (d, J = 16.2 Hz, 1H), 6.22-6.16 (m, 1H), 4.57 (d, J = 5.1 Hz, 2H), 1.93 (br s, 1H);
13C{1H} (125 MHz, CDCl3) δ 137.2, 132.1, 131.3, 129.4, 128.6, 126.6, 126.3, 125.8, 125.4,
125.1, 63.8. ESI-HRMS m/z calcd for C17H15O [M+H]+ 235.1117, found 235.1116.
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3-(Furan-2-yl)prop-2-en-1-ol (4j).37 Yellow oil; 92% yield (114 mg); H NMR (500 MHz,
CDCl3) δ 7.34 (s, 1H), 6.45 (d, J = 15.9 Hz, 1H), 6.37-6.36 (m, 1H), 6.29 (dt, J = 15.8 and 5.6
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Hz, 1H), 6.24-6.23 (d, J = 3.2 Hz, 1H), 4.29 (d, J = 5.5 Hz, 2H), 1.85 (br s, 1H); C{1H} (125
MHz, CDCl3) δ 152.3, 142.0, 127.2, 119.2, 111.2, 107.9, 63.2.
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2-Methylpent-2-en-1-ol (4k).38 Light yellow oil; 80% yield (80 mg); H NMR (500 MHz,
CDCl3) δ 5.42 (td, J = 7.1 and 1.2 Hz, 1H), 4.01 (s, 2H), 2.09-2.03 (m, 2H), 1.67 (s, 3H), 1.22 (d,
J = 6.2 Hz, 1H), 0.98 (t, J = 7.6 Hz, 3H); 13C{1H} (125 MHz, CDCl3) δ 134.0, 128.1, 68.8, 20.8,
14.0, 13.4.
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2-Ethylhex-2-en-1-ol (4l).39 Light yellow oil; 91% yield (116 mg); H NMR (500 MHz,
CDCl3) δ 5.39 (t, J = 7.3 Hz, 1H), 4.06 (s, 2H), 2.13 (q, J = 7.6 Hz, 2H), 2.04 (q, J = 7.4 Hz, 2H),
1.42-1.37 (m, 2H), 1.01 (t, J = 7.6 Hz, 3H), 0.92 (t, J = 7.4 Hz, 3H); 13C{1H} (125 MHz, CDCl3)
δ 1407, 126.4, 66.9, 29.4, 22.9, 21.0, 13.9, 13.2.
Cyclohex-3-enylmethanol (4m).40 Light yellow oil; 93% yield (104 mg); 1H NMR (500 MHz,
CDCl3) δ 5.70-5.65 (m, 2H), 3.55-3.52 (m, 2H), 2.13-2.07 (m, 4H), 1.82-1.71 (m, 3H), 1.29-1.26
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(m, 1H); 13C{1H} (125 MHz, CDCl3) δ 127.1, 125.8, 67.7, 36.2, 28.0, 25.1, 24.6.
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5-Norbornene-2-methanol (4n).41 Light yellow oil; 96% yield (119 mg); 1H NMR (500 MHz,
CDCl3) δ 6.15-6.13 (m, endo, 0.8H), 6.12-6.10 (m, exo, 0.2H), 6.08-6.06 (m, exo, 0.2H), 5.97-
5.95 (m, endo, 0.8H), 3.72 (dd, J = 6.5 and 10.6 Hz, exo, 0.2H), 3.55-3.52 (m, exo, 0.2H), 3.41
(dd, J = 6.6 and 10.4 Hz, endo, 0.8H), 3.27-3.23 (m, endo, 0.8H), 2.93 (s, endo, 0.8H), 2.81 (s,
endo, 0.8H), 2.75 (s, exo, 0.2H), 2.31-2.27 (m, endo, 0.8H), 1.84-1.79 (m, endo, 0.8H), 1.64-1.63
(m, exo, 0.2H), 1.62-1.59 (m, exo, 0.2H), 1.46 (d, J = 7.8 Hz, endo, 0.8H), 1.35-1.33 (m, exo,
0.2H), 1.30-1.27 (m, exo, 0.2H), 1.23-1.20 (m, exo, 0.2H), 1.11 (dt, J = 3.9 and 11.6 Hz, exo,
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0.2H), 0.52 (m, endo, 0.8H); C{1H} (125 MHz, CDCl3) δ 137.3 (endo), 136.7 (exo), 136.4
(exo), 132.1 (endo), 67.4 (exo), 66.4 (endo), 49.4 (endo), 44.9 (exo), 43.5 (endo), 43.2 (exo),
42.1 (endo), 41.8 (exo), 41.6 (endo), 41.4 (exo), 29.5 (exo), 28.7 (endo).
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3,7-Dimethyl-2,6-octadienol (4o).3b Light yellow oil; 94% yield (145 mg); H NMR (500
MHz, CDCl3) δ 5.44-5.39 (m, 1H), 5.11-5.08 (m, 1H), 4.14-4.07 (m, 2H), 2.11-2.02 (m, 4H),
13
1.75-1.60 (m, 10H); C{1H} (125 MHz, CDCl3) δ 139.5 (trans), 139.2 (cis), 132.2 (cis), 131.5
(trans), 124.4 (cis), 123.8 (trans), 123.7 (cis), 123.3 (trans), 59.1 (trans), 58.7 (cis), 39.4 (trans),
31.9 (cis), 26.4 (cis), 26.3 (trans), 25.5 (cis + trans), 23.3 (cis), 17.5 (trans), 17.5 (cis), 16.1
(trans).
Procedure for large-scale transfer hydrogenation of 1a with isopropanol catalyzed by
[Cp*Ir(2,2’-bpyO)(H2O)] (Scheme 3). In a 250-mL Schlenk tube, 1a (2120 mg, 20 mmol),
isopropanol (50 mL), cat. 8 (5.4 mg, 0.01 mmol, 0.05 mol %) were placed under an N2
o
atmosphere, and the reaction mixture was heated at 120 C in an oil bath for 12 h. The mixture
was then cooled to ambient temperature, concentrated in vacuo and purified by flash column
chromatography (hexanes/ethyl acetate = 10/1) to afford the corresponding product 2a (1987 mg,
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18.4 mmol, 92% yield).
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Procedure for transfer hydrogenation of glucose with isopropanol catalyzed by
[Cp*Ir(2,2’-bpyO)(H2O)] (Scheme 4). In a 25-mL Schlenk tube, glucose monohydrate (1
mmol), isopropanol (5 mL), cat. 8 (1.1 mg, 0.2 mol %) were placed under an N2 atmosphere, and
the reaction mixture was heated at 120 oC in an oil bath for 12 h. The mixture was then cooled to
ambient temperature, concentrated in vacuo and purified by recrystallization with ethanol to
afford the corresponding products.
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Sorbitol (6).42 White solid; 80% yield (146 mg); mp 98-99 oC; H NMR (500 MHz, DMSO-
d6) δ 4.54 (d, J = 7.6 Hz, 1H), 4.49-4.46 (m, 2H), 4.38 (d, J = 7.6 Hz, 1H), 4.33 (t, J = 7.6 Hz,
1H), 4.11 (d, J = 7.6 Hz, 1H), 3.66-3.64 (m, 1H), 3.57-3.53 (m, 2H), 3.45-3.33 (m, 5H); 13C{1H}
(125 MHz, DMSO-d6) δ 73.9, 72.4, 71.6, 69.1, 63.6, 62.7.
Procedure for transfer hydrogenation of ketones with isopropanol catalyzed by
[Cp*Ir(2,2’-bpyO)(H2O)] (Table 3). In a 25-mL Schlenk tube, ketons (1 mmol), isopropanol (5
mL), cat. 8 (1.1 mg, 0.2 mol %) were placed under an N2 atmosphere, and the reaction mixture
was heated at 82 oC in an oil bath for 6 h. The mixture was then cooled to ambient temperature,
concentrated in vacuo and purified by flash column chromatography (hexanes/ethyl acetate =
10/1) to afford the corresponding products.
1-Phenylethanol (8a).43 Light yellow oil; 95% yield (116 mg); 1H NMR (500 MHz, CDCl3) δ
7.39-7.34 (m, 4H), 7.29-7.28 (m, 1H), 4.93-4.89 (m, 1H), 1.80 (br s, 1H), 1.51 (d, J = 6.5 Hz,
3H); 13C{1H} (125 MHz, CDCl3) δ 145.8, 128.4, 127.4, 125.3, 70.3, 25.1.
1-M-tolylethanol (8b).43 Light yellow oil; 95% yield (129 mg); 1H NMR (500 MHz, CDCl3)
δ 7.24 (t, J = 7.4 Hz, 1H), 7.19 (s, 1H), 7.17 (d, J = 7.6 Hz, 1H), 7.09 (d, J = 7.5 Hz, 1H), 4.87 (q,
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J = 6.4 Hz, 1H), 2.36 (s, 1H), 1.82 (br s, 1H), 1.49 (d, J = 6.5 Hz, 3H); C{1H} (125 MHz,
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CDCl3) δ 145.8, 138.1, 128.4, 128.2, 126.1, 122.4, 70.4, 25.1, 21.4.
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1-(4-Methoxyphenyl)ethanol (8c).43 Light yellow oil; 86% yield (130 mg); H NMR (500
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MHz, CDCl3) δ 7.31 (d, J = 8.6 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H), 4.87 (q, J = 6.4 Hz, 1H), 3.81
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(s, 3H), 1.73 (br s, 1H), 1.49 (d, J = 6.5 Hz, 3H); C{1H} (125 MHz, CDCl3) δ 158.9, 138.0,
126.6, 113.8, 69.9, 55.2, 25.0.
1-(4-Fluorophenyl)ethanol (8d).43 Light yellow oil; 96% yield (134 mg); 1H NMR (500 MHz,
CDCl3) δ 7.34-7.32 (m, 2H), 7.02 (t, J = 8.7 Hz, 2H), 4.88 (q, J = 6.4 Hz, 1H), 2.01 (br s, 1H),
13
1.47 (dd, J = 2,1 and 6.5 Hz, 3H); C{1H} (125 MHz, CDCl3) δ 163.1 (d, JC-F = 243.8 Hz),
141.5 (d, JC-F = 2.7 Hz), 127.1 (d, JC-F = 8.0 Hz), 115.3, (d, JC-F = 21.3 Hz), 69.7, 25.2.
1-(4-Chlorophenyl)ethanol (8e).43 Light yellow oil; 95% yield (148 mg); 1H NMR (500 MHz,
CDCl3) δ 7.32-7.28 (m, 4H), 4.87 (q, J = 6.5 Hz, 1H), 2.04 (br s, 1H), 1.47 (d, J = 6.5 Hz, 3H);
13C{1H} (125 MHz, CDCl3) δ 144.2, 133.0, 128.6, 126.8, 69.7, 25.2.
1-(3-Bromophenyl)ethanol (8f).43 Light yellow oil; 97% yield (195 mg); 1H NMR (500 MHz,
CDCl3) δ 7.54 (d, J = 1.6 Hz, 1H), 7.40 (d, J = 7.7 Hz, 1H), 7.29 (d, J = 7.7 Hz, 1H), 7.21 (t, J =
7.7 Hz, 1H), 4.87 (q, J = 6.3 Hz, 1H), 1.87 (br s, 1H), 1.49 (dd, J = 2.0 and 6.3 Hz, 3H); 13C{1H}
(125 MHz, CDCl3) δ 148.1, 130.5, 130.1, 128.6, 124.0, 122.6, 69.8, 25.2.
1
1-(4-Nitrophenyl)ethanol (8g).20 Yellow oil; 96% yield (160 mg); H NMR (500 MHz,
CDCl3) δ 8.22 (d, J = 8.8 Hz, 2H), 7.56 (d, J = 8.6 Hz, 2H), 5.03 (t, J = 6.5 Hz, 1H), 2.00 (br s,
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1H), 1.53 (d, J = 6.5 Hz, 3H); C{1H} (125 MHz, CDCl3) δ 153.1, 147.1, 126.1, 123.7, 69.4,
25.4.
4-(1-Hydroxyethyl)benzonitrile (8h).44 Light yellow oil; 95% yield (140 mg); 1H NMR (500
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MHz, CDCl3) δ 7.64 (d, J = 7.8 Hz, 2H), 7.50 (d, J = 8.2 Hz, 2H), 4.97 (q, J = 6.4 Hz, 1H), 2.19
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(br s, 1H), 1.50 (d, J = 6.5 Hz, 3H); C{1H} (125 MHz, CDCl3) δ 151.1, 132.3, 126.0, 118.8,
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111.0, 69.6, 25.4.
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1-Phenylpropan-1-ol (8i).43 Light yellow oil; 92% yield (125 mg); H NMR (500 MHz,
CDCl3) δ 7.35-7.33 (m, 4H), 7.29-7.26 (m, 1H), 4.60 (t, J = 6.6 Hz, 1H), 1.87 (br s, 1H), 1.87-
1.73 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H); 13C{1H} (125 MHz, CDCl3) δ 144.6, 128.4, 127.5, 126.0,
31.9, 10.1.
1-Phenylbutan-1-ol (8j).45 Light yellow oil; 93% yield (140 mg); 1H NMR (500 MHz, CDCl3)
δ 7.35 (d, J = 4.4 Hz, 4H), 7.29-7.26 (m, 1H), 4.68 (t, J = 6.7 Hz, 1H), 1.82-1.76 (m, 2H), 1.72-
1.65 (m, 1H), 1.49-1.39 (m, 1H), 1.36-1.26 (m, 1H), 0.93 (t, J = 7.4 Hz, 3H); 13C{1H} (125 MHz,
CDCl3) δ 144.9, 128.4, 127.5, 125.9, 74.4, 41.2, 19.0, 13.9.
Cyclohexanol (8k).43 Light yellow oil; 82% yield (82 mg); H NMR (500 MHz, CDCl3) δ
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3.62-3.59 (m, 1H), 1.90-1.86 (m, 3H), 1.75-1.72 (m, 2H), 1.57-1.53 (m, 1H), 1.32-1.46 (m, 5H);
13C{1H} (125 MHz, CDCl3) δ 70.2, 35.5, 25.4, 24.1.
Butane-1,3-diol (8l).46 Light yellow oil; 91% yield (82 mg); H NMR (500 MHz, CDCl3) δ
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4.07-4.04 (m, 1H), 3.87-3.77 (m, 2H), 3.53 (br s, 1H), 3.42 (br s, 1H), 1.70-1.66 (m, 2H), 1.24-
1.22 (dd, d, J = 2.9 and 6.2 Hz, 3H); 13C{1H} (125 MHz, CDCl3) δ 67.6, 61.0, 40.4, 23.6.
Notes
The authors declare no competing financial interest.
Acknowledgments
Financial support by National Natural Science Foundation of China (No. 21272115) and Natural
Science Foundation of Jiangsu Province (No. BK20161494) for financial support is greatly
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appreciated.
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Supporting Information.
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1H NMR and C NMR spectra of the products. This material is available free of charge via the
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Internet at http://pubs.acs.org.
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o
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