Chiral thiophosphoramide catalyzed asymmetric aryl transfer reactions for the synthesis of functional diarylmethanols

Article abstract of DOI:10.1016/j.tetasy.2016.11.011

In this investigation, chiral thiophosphoramide 3d was easily prepared from chiral (1R,2R)-1,2-diphenylethylenediamine and then applied as an efficient chiral ligand in the catalytic asymmetric arylation reactions of various aromatic aldehydes. The corresponding diarylmethanol products were produced with good to excellent yields (up to 98%) and enantioselectivities (up to 94%). The recovery of chiral ligand 3d could be as high as 96%.

Full text of DOI:10.1016/j.tetasy.2016.11.011

Tetrahedron: Asymmetry xxx (2016) xxx–xxx
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Chiral thiophosphoramide catalyzed asymmetric aryl transfer
reactions for the synthesis of functional diarylmethanols
a,
Yabai Wang a,b,y, Hua Zong a,y, Huayin Huang a, , Ling Song
⇑
⇑
a The Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian
350002, China
b Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China
a r t i c l e i n f o
a b s t r a c t
Article history:
In this investigation, chiral thiophosphoramide 3d was easily prepared from chiral (1R,2R)-1,2-
diphenylethylenediamine and then applied as an efficient chiral ligand in the catalytic asymmetric
arylation reactions of various aromatic aldehydes. The corresponding diarylmethanol products were
produced with good to excellent yields (up to 98%) and enantioselectivities (up to 94%). The recovery
of chiral ligand 3d could be as high as 96%.
Received 18 September 2016
Revised 7 November 2016
Accepted 14 November 2016
Available online xxxx
Ó 2016 Elsevier Ltd. All rights reserved.
1. Introduction
boron-zinc transmetallation protocol. Since various aryl boronic
acids with functional groups are commercially available or can
The catalytic enantioselective addition of aryl groups to aldehy-
des has attracted great attention.1 The resulting chiral diaryl
methanols are significant backbones of many biologically active
natural products and medicine,2 such as cizolirtine I,3 neobenodine
II,2a,4 carbinoxamine III5 and orphenadrine IV.4,6 In addition, chiral
diarylmethanols can be used to prepare many useful drugs V7 and
VI8,9 through nucleophilic displacement at the stereocenter with-
out the loss of enantiomeric purity (Fig. 1).
The catalytic asymmetric addition of arylmetal reagents to aro-
matic aldehydes is been regarded as one of the most useful and
straightforward methods for the synthesis of enantioenriched diar-
lymethanols by CAC bond formation.1,10 Over the past few dec-
ades, great progress has been achieved in the asymmetric
addition of arylaluminiums,11 aryl-Grignard reagents,12 arylsilane
reagents,13 aryl titanium reagents14 and aryl lithium reagents15
to aromatic aldehydes. Compared with the above developed meth-
ods, the asymmetric addition of arylzinc reagents1,16–18 has advan-
tages of wide substituent tolerance and mild reaction conditions
due to the relatively low reactivity of arylzinc reagents. In 2002,
Bolm et al. developed a significant arylation method for the cat-
alyzed asymmetric synthesis of chiral secondary diarylmethanols
with excellent enantioselevtivities.19 The active arylzinc species
used in the asymmetric arylation, were generated in situ from a
be easily prepared, the scope of aryl boronic acids as aryl sources
has been extensively explored and many efficient asymmetric pro-
tocols have been developed.20,21 Despite the pioneering studies
that have been reported on the catalytic asymmetric addition of
aryl zinc reagents to aromatic aldehydes, the development of
highly efficient asymmetric catalyst systems with wide substrate
tolerance using easily prepared chiral ligands is still desirable.
Chiral 1,2-diamino phosphoramide ligands are very efficient in
organozinc reagent catalytic asymmetric reactions,17m,20d,22–24
organocatalyzed asymmetric reactions25 and enantiodiscrimination
of chiral acids.26 To explore the application of chiral phospho-
ramide-Zn(II) ligands, we herein report examples of catalytic asym-
metric arylation reactions from arylboronic acids and aromatic
aldehydes for the synthesis of chiral secondary diarylmethanols.
2. Results and discussion
Systematic studies of a model reaction comprising 4-methyl
benzaldehyde, phenyl boronic acid, dialkylzinc reagent and a chiral
ligand, are summarized in Table 1. The phenylzinc reagent was
prepared in situ by heating a mixture of dimethyl zinc and phenyl
boronic acid in toluene for 12 h at 60 °C. The effect of the chiral
ligand was first screened. As shown in Table 1, the corresponding
diarylmethanol 4a was formed with high yield and moderate enan-
tioselectivity in the presence of quinine derived phosphoramide
chiral ligand 1 (Table 1, entry 1). The reaction using chiral
(1R,2R)-1,2-diaminocyclohexane derived phosphoramide 2 pro-
ceeded to give 4a with 90% yield and 64% ee (Table 1, entry 2).
⇑
Corresponding authors. Tel.: +86 591 83720913; fax: +86 591 83722697.
E-mail addresses: huanghuayin@fjirsm.ac.cn (H. Huang), songling@fjirsm.ac.cn
(L. Song).
y
These authors contributed equally.
http://dx.doi.org/10.1016/j.tetasy.2016.11.011
0957-4166/Ó 2016 Elsevier Ltd. All rights reserved.
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Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
NMe2
O
NMe2
O
NMe2
O
O
NMe2
NMe2
O
MeO
N
Ph
Cl
N
N
Ph
Ph
Cl
Ph
N
N
I
II
IV
V
VI
III
Figure 1. Structures of biologically active diarylmathanol derivatives.
Table 1
Catalytic asymmetric phenyl transfer from boronic acid to 4-methyl benzaldehyde using a phosphoramide chiral liganda
O
OH
Me2Zn (10 equiv)
ligand (20 mol%)
H
PhB(OH)2
(2 equiv)
+
toluene/hexane = 1:1
0 oC~r.t., 24 h
4a
H
X
H
Ph
Ph
N
H
Ph2P
N
X
X
MeO
N
R2
Ph2P NH
Ph2P NH
N
R2
R1
R1
1
2
3a-3d
N
Entry
Ligand
X
NR1R2
Yieldb (%)
eec (%)
1
2
3
4
5
6
1
2
3a
3b
3c
3d
O
O
O
O
O
S
—
89
90
94
87
89
92
55
64
34
70
77
78
NHiPr
NEt2
NHBn
NHiPr
NHiPr
a
b
c
Unless otherwise noted, all reactions were carried out with benzaldehyde on a 0.5 mmol scale.
Isolated yields.
Determined by chiral GC analysis and the absolute configuration was assigned by comparison of the sign of specific rotation value with the literature value.
Chiral (1R,2R)-1,2-diphenylethylenediamine derived N,N-diethyl
substituted phosphoramide 3a gave the diarylmethanol 4a with
excellent yield but only 34% ee (Table 1, entry 3). N-Benzyl mono-
substituted phosphoramide 3b exhibited higher stereoselectivity
for the asymmetric aryl transfer reaction (Table 1, entry 4). When
N-isopropyl monosubstituted phosphoramide 3c was used, the
diarylmethanol 4a was afforded with 87% yield and 77% ee (Table 1,
entry 5). Finally, N-isopropyl monosubstituted thiophosphoramide
3d proved to be the optimal chiral ligand, and under the same reac-
tion conditions, afforded 4a with 92% yield and 78% ee (Table 1,
entry 6). As a result, chiral thiophosphoramide 3d was identified
as the best chiral ligand for the catalytic asymmetric phenyl trans-
fer reaction.
The reaction conditions, such as the solvent, reaction tempera-
ture, dialkyl zinc reagent and the amount of the chiral ligand were
further optimized. The results are listed in Table 2. Various sol-
vents, such as toluene, hexane, THF and MTBE, were also evalu-
ated; the mixed solvent (toluene/hexane = 1:1) was found to be
the best solvent giving 92% yield with 78% ee of the product
(Table 2, entries 1–5). The effect of the temperature was then
investigated. The yield and ee increased slightly when the reaction
temperature was decreased (Table 2, entries 6 and 7). When
decreasing the temperature to ꢀ40 °C, diarylmethanol 4a was
obtained with 85% yield and 82% ee (Table 2, entry 8). If the
dimethylzinc reagent was replaced by diethylzinc reagent, the cor-
responding alcohol product was afforded with 90% yield and 83%
ee (Table 2, entry 9). Increasing the loading of chiral ligand to
30 mol %, excellent enantioselectivity of the product was obtained
(93% ee, Table 2, entry 10). When 40 mol % of chiral ligand 3d was
used, almost no further improvement on yield and ee of the pro-
duct was observed (Table 2, entry 11). Thus, the model reaction
was best performed using 2 equiv of phenyl boronic acid and
10 equiv of Et2Zn with 30 mol % chiral ligand 3d in mixed solvent
(toluene/hexane = 1:1) at ꢀ40 °C for 24 h. To achieve high enan-
tioselectivity, high loading of the chiral ligand 3d (30 mol %) was
required, but it can be recovered by flash column chromatography
without any loss of purity. The recovery of chiral ligand 3d could be
as high as 96%.
With the optimized conditions in hand, we next investigated
the substrate scope and limitation of the asymmetric arylation
reaction system using 30 mol % chiral ligands 3d. The results are
listed in Table 3.
The asymmetric arylation of a variety of aromatic aldehydes
with in situ generated aryl zinc reagents took place, affording the
anticipated chiral diarylmethanols products in good to excellent
yields (81–98% yields) and with good to excellent enantioselectiv-
ity (82–94% ee) (Table 3, entries 1–10). Aromatic aldehydes with
electron-withdrawing or electro-donating substituents at the
ortho-, meta-, and para-positions of the benzene rings worked well.
This catalytic asymmetric reaction system also worked well when
1-naphthaldehdye or 2-naphthaldehdye was used as the substrate
(Table 3, entries 11 and 12). When 2-thiophenaldehyde was used
as substrate 90% yield and 51% ee were obtained (Table 3, entries
13). As shown in Table 3, entries 14–16, other aryl transferring
reagents also reacted very smoothly, and the corresponding chiral
diarylmethanols products could be obtained with good yields and
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Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
3
Table 2
Optimization of the reaction conditions for the catalytic asymmetric phenyl transfer from boronic acid to 4-methyl benzaldehyde using chiral ligand 3da
O
OH
R2Zn (10 equiv)
ligand 3d (y mol%)
H
PhB(OH)2
(2 equiv)
+
solvent, temp., 24 h
4a
Entry
y (mol %)
R
Temp.
Solvent
Yieldb (%)
eec (%)
1d
2
3
20
20
20
20
20
20
20
20
20
30
40
Me
Me
Me
Me
Me
Me
Me
Me
Et
0 °C–rt
0 °C–rt
0 °C–rt
0 °C–rt
0 °C–rt
ꢀ10 °C
ꢀ20 °C
ꢀ40 °C
ꢀ40 °C
ꢀ40 °C
ꢀ40 °C
Toluene/hexane
Toluene
Hexane
Hexane/MTBE
Hexane/THF
Toluene/hexane
Toluene/hexane
Toluene/hexane
Toluene/hexane
Toluene/hexane
Toluene/hexane
92
91
88
86
Trace
90
91
85
90
91
78
76
77
75
N.D.e
79
81
82
83
93
93
4d
5d
6d
7d
8d
9d
10d,f
11d
Et
Et
93
a
b
c
d
e
f
Unless otherwise noted, all reactions were carried out with benzaldehyde on a 0.5 mmol scale.
Isolated yields.
Determined by chiral GC analysis and the absolute configuration was assigned by comparison of the sign of specific rotations with the literature values.
The ratio of the solvent volume was 1:1.
Not determined.
The chiral ligand can be recovered with 96% yield.
excellent enantioselectivities. Several functionalized aryl boronic
acids were used as aryl transfer reagents in the catalytic asymmet-
ric addition to various aromatic aldehydes with functional groups.
Excellent yields (90–95% yields) and good to excellent enantiose-
lectivities (80–92% ee) could be attained (Table 3, entries 17–22).
It is noteworthy that the ester group can be tolerated in this cat-
alytic asymmetric aryl transfer system (entry 21).
Compared with aromatic aldehydes, aliphatic aldehydes are less
active and enantioselective. Thus, many excellent chiral ligands,
which are highly efficient to aromatic aldehydes, are less effective
towards aliphatic aldehydes.27 When 3-methylbutyraldehyde and
phenyl boronic acid were used as the substrate and aryl transfer
reagent respectively, the corresponding product (S)-3-methyl-1-
phenylbutan-1-ol was obtained with 79% yield and 55% ee under
the optimized reaction conditions.
sured on a polarimeter and specific rotations are reported as fol-
lows: ½a TD
ꢁ
(c g/100 mL, solvent). GC analysis was performed on a
gas chromatograph with a FID detector on fused silica chiral capil-
lary column (Chirasil Dex CB column, 25 m Length ꢂ 0.32 mm
ID ꢂ 0.25 mm film thickness). The high performance liquid chro-
matography (HPLC) analysis was performed using Chiralcel OD-
H, AD-H, OJ-H or AS-H column. Chiral ligands 1,23f 2,23h 3a,23c
3b,23b and 3c23b were prepared according to the literature values.
Compound 523e was synthesized according to reported method.
4.2. Preparation of chiral ligand 3d
Ph
N
Ph
1. N2H4.H2O, EtOH
reflux, 1 h
O
Ph
Ph
NHi-Pr
3. Conclusions
S
O
Ph2P(=S)Cl, Et3N
CH2Cl2, 4 h
2.
Ph2P NH
3d
NHi-Pr
In conclusion, thiophosphoramide 3d was easily prepared from
chiral 1, 2-diphenylethylenediamine and was identified as an
efficient chiral ligand in the catalytic asymmetric arylation of alde-
hydes. Using this protocol, various chiral functionalized diaryl-
methanols with high enantioselectivities could be prepared
conveniently from commercially available aryl boronic acids and
aldehydes.
5
To a solution of 5 (845 mg, 2.2 mmol) in ethanol (3 mL), hydra-
zine monohydrate (0.97 mL, 20 mmol) was added, and the reaction
mixture was stirred at reflux (oil bath, 85 °C) for 2 h. After the
resultant mixture was cooled to room temperature, diethyl ether
(30 mL) and CH2Cl2 (30 mL) were added to form precipitates,
which were removed by filtration. The filtrate was dried over anhy-
drous MgSO4, and the solvent was removed under reduced pres-
sure to afford 508 mg of white solid, which was used in the next
step without further purification. A reaction mixture of the white
solid in CH2Cl2 (15 mL) with Et3N (556 mg, 5.5 mmol) was stirred
at room temperature for 15 min. After being cooled to 0 °C, it
4. Experimental
4.1. General
All experiments were carried out in dried glassware with mag-
netic stirring under an atmosphere of dry nitrogen. 1H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were recorded in CDCl3
solutions using a 400 MHz spectrometer. Chemical shifts are
reported in parts per million (ppm, d) relative to CDCl3 (d 7.26
for 1H NMR), or CDCl3 (d 77.0 for 13C NMR). Multiplicities are indi-
cated as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet)
and br (broad). Commercial reagents were used as received unless
otherwise indicated. All solvents were purified and dried prior to
use according to standard methods. Optical rotations were mea-
was added to
a solution of diphenylthiophosphinic chloride
(1.26 g, 5.0 mmol) in dry CH2Cl2 (15 mL) dropwise and stirred for
30 min at 0 °C. The temperature was allowed to warm to room
temperature and then kept at room temperature for approximately
5 h. After the reaction mixture was cooled to 0 °C, water (30 mL)
and CH2Cl2 (30 mL) were added. The organic layer was dried over
anhydrous MgSO4 and concentrated. The crude product was sub-
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4
Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
Table 3
Asymmetric arylation of aromatic aldehydesa
Et2Zn (10 equiv)
OH
ligand 3d (30 mol%)
Ar1CHO
+
Ar2B(OH)2
(2 equiv)
Ar1
Ar2
toluene/hexane = 1:1
-40 oC, 24 h
4
Entry
1
Product
Name
Yieldb (%)
91
eec (%)
OH
(R)-4a
93
OMe OH
2
3
(R)-4b
(R)-4c
95
98
84
84
OH
MeO
OH
4
5
(R)-4d
(R)-4e
93
92
94
92
OH
Br
OH
OH
6
(R)-4f
96
84
Br
7
8
9
(R)-4g
(R)-4h
(R)-4i
88
81
90
Cl
F
OH
93
OH
83 (82d)
87 (81d)
F
OH
10
11
(R)-4j
95 (93d)
90 (84d)
F3C
OH
(R)-4k
86
82
OH
12
13
14
(R)-4l
82
90
85
87
51
91
OH
OH
OH
(R)-4m
(S)-4a
S
15
(S)-4g
92
89
Cl
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Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
5
Table 3 (continued)
Entry
Product
Name
Yieldb (%)
84
eec (%)
OH
OH
16
17
18
19
(S)-4l
86
(R)-4n
(R)-4o
90
92
91
91
92
90
Cl
OH
OH
(S)-4p
F
OH
Br
20
21
(R)-4q
90
93
95
89
80
92
F
OH
(S)-4r
MeO
O
F
OH
22
(R)-4s
t-Bu
a
Unless otherwise noted, all reactions were carried out with benzaldehyde on a 0.5 mmol scale.
Isolated yields.
Determined by chiral GC or HPLC analysis.
b
c
d
1.3 equiv PhB(OH)2, 6.5 equiv Et2Zn and 15 mol % chiral ligand 3d were used.
jected to silica gel column chromatography (EtOAc/hexane = 3/1),
which afforded 703 mg (68%) of 3d as a white solid. Mp, 162–
163 °C; [
30.9 = +4.9 (c 1.00, CH2Cl2); 1H NMR (400 MHz, CDCl3):
riched secondary alcohol. The ee value of the secondary alcohol
was determined by chiral GC or HPLC. The absolute configuration
of the alcohol was assigned as (R) or (S) by comparison of the speci-
fic rotation data with the reported literature data.
a]
D
d 0.97 (t, J = 6.4 Hz, 6H), 1.64 (s, 1H), 2.55–2.68 (m, 1H), 3.93 (d,
J = 8.2 Hz, 1H), 4.47–4.57 (m, 1H), 4.62 (d, J = 4.0 Hz, 1H), 6.87–
7.27 (m, 13H), 7.36–7.54 (m, 3H), 7.61–7.76 (m, 2H), 7.81–7.98
(m, 2H); 13C NMR (100 MHz, CDCl3): d 21.9, 24.4, 45.3, 61.2, 65.7
(d, J = 8.0 Hz), 126.8, 127.2, 127.50, 127.54, 127.7, 128.0, 128.1,
128.27, 128.34, 128.5, 131.0, 131.1, 131.5, 132.1, 132.2, 132.7,
133.8, 134.7, 135.8, 140.2, 140.7; 31P NMR (162 MHz, CDCl3): d
60.5; HRMS (ESI): (m/z) [M+H]+ calcd for C29H32N2SP, 471.1946;
found, 471.1945.
4.3.1. (4-Methylphenyl)(phenyl)methanol 4a15d
91% yield and 93% ee were obtained. [a]
30 = +3.8 (c 1.0, CHCl3)
D
(Lit.15d
[a
]
D
25 = ꢀ5 (c 1.0, CHCl3) for 94% ee (S)); the ee value was
determined by Chiral GC Chirasil Dex CB [Column temperature:
135 °C, tR = 95.3 min (R), tR = 102.0 min (S)]. 1H NMR (400 MHz,
CDCl3): d 2.42 (s, 3H), 3.15 (br, 1H), 5.80 (s, 1H), 7.18–7.24 (m,
2H), 7.29–7.36 (m, 3H), 7.37–7.46 (m, 4H); 13C NMR (100 MHz,
CDCl3): d 21.2, 76.1, 126.5, 127.5, 128.5, 129.2, 137.3, 141.0, 144.0.
4.3. General procedure for the catalytic asymmetric arylation of
aldehyde
4.3.2. 2-Methoxyphenyl(phenyl)methanol 4b28
95% yield and 84% ee were obtained. [
a]
25.8 = +16.7 (c 1.0, CHCl3)
D
Under an N2 atmosphere, to a reaction tube which contained
arylboronic acid (1.0 mmol) and toluene (2 mL) was added
diethylzinc (5.0 mmol, 1.0 M in hexane) at room temperature,
and then heated at 60 °C for 12 h. After the flask was cooled to
rt, the reaction mixture was added to another schlenk tube, which
contained the chiral ligand (0.15 mmol) and toluene (3 mL), and
the resulting mixture was stirred for 30 min. Aldehyde (0.5 mmol)
was then added immediately to the mixture at ꢀ40 °C. The mixture
was stirred for 24 h at ꢀ40 °C and quenched by adding aqueous
HCl (1.0 M, 5 mL). Extraction with EtOAc (10 mL ꢂ 3) gave the
combined organic layers, which were washed with brine (10 mL),
dried over MgSO4 and concentrated in vacuo to give a residue,
which was subjected to silica gel column chromatography
(EtOAc/hexane = 1/10), affording the corresponding enantioen-
(Lit.28 20 = +22.8 (c 1.27, CHCl3) for 70% ee (R)); the ee value was
[a]
D
determined on a Daicel Chiralcel OD-H column [(10% IPA/hexane,
1.0 mL/min, retention time: 9.2 min (minor) and 10.2 min (major)),
tR = 9.2 min (S), tR = 10.2 min (R)]. 1H NMR (400 MHz, CDCl3): d 3.22
(d, J = 4.2 Hz, 1H), 3.84 (s, 3H), 6.12 (s, 1H), 6.90–7.05 (m, 2H),
7.27–7.49 (m, 7H); 13C NMR (100 MHz, CDCl3): d 55.5, 72.2,
110.7, 121.1, 123.8, 126.6, 127.2, 127.8, 128.2, 128.7, 132.2,
136.1, 143.5, 149.8, 156.7.
4.3.3. 4-Methoxyphenyl(phenyl)methanol 4c15d
98% yield and 84% ee were obtained, [a]
26.3 = +6.6 (c 1.0, CHCl3)
D
(Lit.15d
[a
]
D
25 = ꢀ19 (c 1.0, CHCl3) for 92% ee (S)); the ee value was
determined on a Daicel Chiralcel AD-H column [(10% IPA/hexane,
0.8 mL/min, retention time: 14.0 min (major) and 15.0 min
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6
Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
(minor)), tR = 14.0 min (R), tR = 15.0 min (S)]. 1H NMR (400 MHz,
CDCl3): d 2.32 (d, J = 3.1 Hz, 1H), 3.81 (s, 3H), 5.83 (s, 1H), 6.85–
6.96 (m, 2H), 7.23–7.495 (m, 7H); 13C NMR (100 MHz, CDCl3): d
55.3, 75.8, 113.9, 126.4, 127.2, 127.5, 127.9, 128.5, 136.2, 144.0,
159.0.
7.70 (m, 9H); 13C NMR (100 MHz, CDCl3): d 75.6, 115.2, 115.4,
126.5, 127.8, 128.2, 128.3, 128.6, 139.6, 143.7, 160.9, 163.4. 19F
CPD NMR (376 MHz, CDCl3): d ꢀ115.04.
4.3.10. (4-(Trifluoromethyl)phenyl)phenylmethanol 4j15d
95% yield and 90% ee were obtained. [
a]
D
30.7 = ꢀ23.1 (c 1.0,
4.3.4. (2-Methylphenyl)(phenyl)methanol 4d29
CHCl3) (Lit.15d
[
a]
25 = +27 (c 1.0, CHCl3) for 90% ee (S)); the ee
D
93% yield and 94% ee were obtained. [
a]
25.1 = +6.3 (c 1.0, CHCl3)
value was determined by Chiral HPLC analysis with a Chiralcel
OJ-H column [(hexane/2-propanol = 90/10, 0.8 mL/min, 220 nm);
retention time: 12.7 min (major) and 13.2 min (minor)),
tR = 12.7 min (R), tR = 13.2 min (S)]. 1H NMR (400 MHz, CDCl3): d
3.22 (s, 1H), 5.79 (m, 1H), 7.31–7.43 (m, 5H), 7.45–7.56 (m, 2H),
7.57–7.73 (m, 2H); 13C NMR (100 MHz, CDCl3): d 75.7, 124.2 (q,
J = 272.1 Hz), 125.4 (q, J = 3.8 Hz), 126.69, 126.71, 128.1, 128.8,
129.6 (q, J = 32.4 Hz), 143.1, 147.5. 19F NMR (376 MHz, CDCl3): d
ꢀ62.4 (s).
D
(Lit.29 20 = +6.8 (c 1.0, CHCl3) for 97% ee (R)). The ee value was
[a]
D
determined on a Daicel Chiralcel OD-H column [(10% IPA/hexane,
1.0 mL/min, retention time: 7.5 min (major) and 7.9 min (minor)),
tR = 7.5 min (R), tR = 7.9 min (S)]. 1H NMR (400 MHz, CDCl3): d 2.19
(br, 1H), 2.28 (s, 3H), 6.03 (s, 1H), 7.12–7.61 (m, 9H); 13C NMR
(100 MHz, CDCl3): d 19.4, 73.4, 126.1, 126.3, 127.1, 127.5, 127.6,
128.5, 130.5, 135.4, 141.5, 142.9.
4.3.5. (3-Bromophenyl)(phenyl)methanol 4e20i
92% yield and 92% ee were obtained. [
a
]
D
28.1 = ꢀ11.0 (c 2.0,
4.3.11. Naphthalen-1-yl(phenyl)methanol 4k15d
CHCl3) (Lit.20i
[
a]
25 = +25.7 (c 0.944, CHCl3) for 87% ee (S)); the ee
86% yield and 82% ee were obtained. [a]
30.5 = +25.6 (c 1.0, CHCl3)
D
D
value was determined on a Daicel Chiralcel AS-H column [(8%
IPA/hexane, 1 mL/min, retention time: 7.0 min (minor) and
7.3 min (major)), tR = 7.0 min (S), tR = 7.3 min (R)]. 1H NMR
(400 MHz, CDCl3): d 2.56 (s, 1H), 5.79 (s, 1H), 7.18–7.45 (m, 8H),
7.53–7.63 (m, 1H); 13C NMR (100 MHz, CDCl3): d 75.6, 115.3,
120.7, 122.6, 125.1, 126.6, 128.0, 128.8, 129.6, 130.1, 130.6,
143.2, 146.0.
(Lit.15d
[a
]
D
25 = ꢀ42 (c 1.0, CHCl3) for 96% ee (S)); the ee value was
determined by Chiral HPLC analysis with a Chiralcel OJ-H column
[(hexane/2-propanol = 80/20, 0.8 mL/min, 220 nm); retention
time: 13.4 min (minor) and 16.9 min (major)), tR = 13.4 min (S),
tR = 16.9 min (R)]. 1H NMR (400 MHz, CDCl3): d 3.00 (s, 1H), 6.48
(s, 1H), 7.27–7.61 (m, 8H), 7.63–7.72 (m, 1H), 7.83–8.00 (m, 2H),
8.02–8.13 (m, 1H); 13C NMR (100 MHz, CDCl3): d 73.6, 124.1,
124.7, 125.4, 125.7, 126.2, 127.2, 127.7, 128.5, 128.6, 128.9,
129.6, 130.8, 134.0, 138.9, 143.2.
4.3.6. (4-Bromophenyl)(phenyl)methanol 4f15d
96% yield and 84% ee were obtained, [
a]
26.5 = ꢀ15.2 (c 1.0,
D
CHCl3) (Lit.15d
[
a]
25 = +19 (c 1.0, CHCl3) for 91% ee (S)); the ee
4.3.12. Naphthalen-2-yl(phenyl)methanol 4l15d
D
value was determined on a Daicel Chiralcel AD-H column [(5%
IPA/hexane, 0.8 mL/min, retention time: 16.1 min (major) and
17.7 min (minor)), tR = 16.1 min (R), tR = 17.7 min (S)]. 1H NMR
(400 MHz, CDCl3): d 3.64 (s, 1H), 5.65 (s, 1H), 7.17–7.25 (m, 2H),
7.31–7.43 (m, 5H), 7.45–7.52 (m, 2H); 13C NMR (100 MHz,
CDCl3): d 75.5, 121.4, 126.7, 127.9, 128.4, 128.7, 131.6, 142.8,
143.4.
82% yield and 87% ee were obtained. [
a
]
D
30.8 = ꢀ5.5 (c 1.0, CHCl3)
(Lit.15d
[a]
25 = +6 (c 1.0, CHCl3) for 90% ee (S)); the ee value was
D
determined by Chiral HPLC analysis with
a Chiralcel OD-H
column [(hexane/2-propanol = 90/10, 0.8 mL/min, 220 nm);
retention time: 16.3 min (minor) and 19.3 min (major)),
tR = 16.3 min (S), tR = 19.3 min (R)]. 1H NMR (400 MHz, CDCl3): d
3.00 (s, 1H), 6.00 (s, 1H), 7.28–7.64 (m, 8H), 7.77–8.00 (m, 4H);
13C NMR (100 MHz, CDCl3): d 76.3, 124.9, 125.2, 126.1, 126.2,
126.8, 127.7, 127.8, 128.2, 128.4, 128.6, 133.0, 133.3, 143.7.
4.3.7. (4-Chlorophenyl)(phenyl)methanol 4g15d
88% yield and 90% ee were obtained. [
a
]
D
27.4 = ꢀ5.3 (c 1.0, CHCl3)
(Lit.15d
[a
]
D
25 = +19 (c 1.0, CHCl3) for 92% ee (S)); the ee value was
4.3.13. Phenyl(thiophen-2-yl)methanol 4m15d
determined on a Daicel Chiralcel AD-H column [(5% IPA/hexane,
0.8 mL/min, retention time: 17.9 min (minor) and 18.5 min
(major)), tR = 17.9 min (S), tR = 18.5 min (R)]. 1H NMR (400 MHz,
CDCl3): d 3.68 (s, 1H), 5.67 (s, 1H), 7.26–7.33 (m, 2H), 7.34–7.49
(m, 7H); 13C NMR (100 MHz, CDCl3): d 75.6, 126.6, 127.9, 128.6,
128.7, 133.3, 142.4, 143.4.
90% yield and 51% ee were obtained. [
a]
D
21.0 = ꢀ11.5 (c 1.0,
CHCl3) (Lit.15d
[
a]
24 = +27 (c 1.0, CHCl3) for 96% ee (S)); the ee
D
value was determined by Chiral HPLC analysis with a Chiralcel
OD-H column [(hexane/2-propanol = 92/8, 0.8 mL/min, 220 nm);
retention time: 10.4 min (minor) and 10.8 min (major)),
tR = 10.4 min (R), tR = 10.8 min (S)]. 1H NMR (400 MHz, CDCl3): d
3.78 (d, J = 2.6 Hz, 1H), 6.00 (s, 1H), 6.89–7.10 (m, 2H), 7.29–7.59
(m, 6H); 13C NMR (100 MHz, CDCl3): d 72.3, 125.1, 125.5, 126.6,
126.8, 128.0, 128.6, 143.4, 148.4.
4.3.8. (3-Fluorophenyl)(phenyl)methanol 4h30
81% yield and 93% ee were obtained. [
a]
26.6 = ꢀ14.3 (c 1.0,
D
CHCl3); the ee value was determined on a Daicel Chiralcel OD-H
column [(5% IPA/hexane, 0.8 mL/min, retention time: 17.8 min
(minor) and 18.4 min (major)), tR = 17.8 min (S), tR = 18.4 min
(R)]. 1H NMR (400 MHz, CDCl3): d 3.54 (s, 1H), 5.74 (s, 1H), 6.97–
7.10 (m, 1H), 7.12–7.26 (m, 2H), 7.28–7.54 (m, 6H); 13C NMR
(100 MHz, CDCl3): d 75.7, 113.3, 113.5, 114.2, 114.5, 122.0, 126.6,
128.0, 128.7, 129.9, 130.0, 143.3, 146.3, 161.7, 164.2. 19F CPD
NMR (376 MHz, CDCl3): d ꢀ112.71.
4.3.14. (4-Chlorophenyl)(o-tolyl)methanol 4n31
90% yield and 91% ee were obtained, [
a]
23.8 = ꢀ5.6 (c 1.0, CHCl3);
D
the ee value was determined on a Daicel Chiralcel AD-H column
[(5% IPA/hexane, 1.0 mL/min, retention time: 10.30 min (major)
and 10.79 min (minor)), tR = 10.30 min (R), tR = 10.79 min (S)]. 1H
NMR (400 MHz, CDCl3): d 2.27 (s, 3H), 2.29 (s, 1H), 5.99 (d,
J = 3.4 Hz, 1H), 7.16–7.21 (m, 1H), 7.22–7.35 (m, 6H), 7.44–7.52
(m, 1H); 13C NMR (100 MHz, CDCl3): d 19.4, 72.8, 126.29, 126.33,
127.8, 128.5, 128.6, 130.7, 133.3, 135.4, 141.3.
4.3.9. (4-Fluorophenyl)(phenyl)methanol 4i15d
83% yield and 87% ee were obtained. [
a]
27.5 = ꢀ6.3 (c 1.0, CHCl3)
D
(Lit.15d
[a
]
D
25 = +8 (c 1.0, CHCl3) for 92% ee (S)); the ee value was
4.3.15. Mesityl(p-tolyl)methanol 4o32
determined on a Daicel Chiralcel AS-H column [(8% IPA/hexane,
0.8 mL/min, retention time: 8.7 min (minor) and 9.0 min
(major)), tR = 8.7 min (S), tR = 9.0 min (R)]. 1H NMR (400 MHz,
CDCl3): d 2.33 (d, J = 3.6 Hz, 1H), 5.85 (d, J = 3.0 Hz, 1H), 6.90–
92% yield and 92% ee were obtained, [a]
24.0 = +39.0 (c 1.0,
D
CHCl3); the ee value was determined on a Daicel Chiralcel OD-H
column [(10% IPA/hexane, 1.0 mL/min, retention time: 5.32 min
(minor) and 5.82 min (major)), tR = 5.32 min (S), tR = 5.82 min
Please cite this article in press as: Wang, Y.; et al. Tetrahedron: Asymmetry (2016), http://dx.doi.org/10.1016/j.tetasy.2016.11.011

Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
7
(R)]. 1H NMR (400 MHz, CDCl3): d 2.28 (s, 3H), 2.30 (s, 6H), 2.34 (s,
3H), 2.39 (s, 3H), 6.34 (d, J = 3.8 Hz, 1H), 6.92 (s, 2H), 7.09–7.28 (m,
4H); 13C NMR (100 MHz, CDCl3): d 20.6, 20.9, 21.1, 71.0, 125.5,
128.9, 130.1, 136.1, 136.6, 137.1, 137.2, 140.1.
nese Academy of Sciences (No. XDB20000000) and The Key Labora-
tory of Coal to Ethylene Glycol and Its Related Technology, Fujian
Institute of Research on the Structure of Matter, Chinese Academic
of Sciences.
4.3.16. (4-Fluorophenyl)(p-tolyl)methanol 4p33
22.8 = +6.2 (c 1.0, CHCl3);
A. Supplementary data
91% yield and 90% ee were obtained, [a]
D
the ee value was determined on a Daicel Chiralcel OD-H column
[(5% IPA/hexane, 0.8 mL/min, retention time: 10.03 min (major)
and 11.50 min (minor)), tR = 10.03 min (S), tR = 11.50 min (R)]. 1H
NMR (400 MHz, CDCl3): d 2.40 (s, 3H), 2.88 (s, 1H), 5.74 (s, 1H),
6.99–7.10 (m, 2H), 7.16–7.22 (m, 2H), 7.23–7.28 (m, 2H), 7.30–
7.39 (m, 2H); 13C NMR (100 MHz, CDCl3): d 21.2, 75.4, 115.2 (d,
J = 21.4 Hz), 126.5, 128.2 (d, J = 8.1 Hz), 129.3, 137.5, 139.8 (d,
J = 3.0 Hz), 140.8, 162.1 (d, J = 245.0 Hz); 19F NMR (376 MHz,
CDCl3): d ꢀ115.2 (m).
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetasy.2016.11.
011.
References
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4.3.17. (3-Bromophenyl)(4-fluorophenyl)methanol 4q12a
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22.9 = ꢀ8.2 (c 1.0, CHCl3);
D
the ee value was determined on a Daicel Chiralcel OD-H column [(5%
IPA/hexane, 0.8 mL/min, retention time: 14.47 min (minor) and
17.28 min (major)), tR = 14.47 min (S), tR = 17.28 min (R)]. 1H NMR
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7.14–7.35 (m, 4H), 7.38–7.47 (m, 1H), 7.52 (s, 1H); 13C NMR
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(d, J = 8.1 Hz), 129.4, 130.2, 130.8, 138.2 (d, J = 3.0 Hz), 145.8, 162.3
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4r20m
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D
22.5 = ꢀ11.4 (c 1.0,
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CHCl3); the ee value was determined on a Daicel Chiralcel OD-H
column [(4% IPA/hexane, 1.0 mL/min, retention time: 23.78 min
(major) and 25.54 min (minor)), tR = 23.78 min (S), tR = 25.54 min
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(s, 1H), 6.95–7.05 (m, 2H), 7.26–7.35 (m, 2H), 7.39–7.46 (m, 2H),
7.97–8.01 (m, 2H); 13C NMR (100 MHz, CDCl3): d 52.2, 75.1,
115.4 (d, J = 21.4 Hz), 126.3, 128.4 (d, J = 8.2 Hz), 129.2, 129.8,
139.1 (d, J = 3.0 Hz), 148.8, 162.2 (d, J = 246.4 Hz), 167.1; 19F NMR
(376 MHz, CDCl3): d ꢀ114.4 (m).
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4.3.19. (4-tert-Butylphenyl)(naphthalen-3-yl)methanol 4s34
95% yield and 92% ee were obtained, [
a]
22.2 = ꢀ8.8 (c 1.0, CHCl3);
D
the ee value was determined on a Daicel Chiralcel AD-H column
[(6% IPA/hexane, 1.0 mL/min, retention time: 12.25 min (minor)
and 13.45 min (major), tR = 12.25 min (S), tR = 13.45 min (R)]. 1H
NMR (400 MHz, CDCl3): d 1.32 (s, 9H), 2.37 (s, 1H), 6.02 (s, 1H),
7.33–7.43 (m, 4H), 7.45–7.55 (m, 3H), 7.78–7.99 (m, 4H); 13C
NMR (100 MHz, CDCl3): d 31.3, 34.5, 76.2, 124.81, 124.85, 125.5,
125.9, 126.2, 126.5, 127.7, 128.1, 128.3, 132.9, 133.3, 140.8, 141.2.
4.3.20. 3-Methyl-1-phenylbutan-1-ol35
79% yield and 55% ee were obtained, [
a]
22.3 = ꢀ11.3 (c 1.0, CH3-
D
CH2OH); the ee value was determined by Chiral GC Chirasil Dex CB
[Column temperature: 140 °C, tR = 7.65 min (S), tR = 8.09 min (R)].
1H NMR (400 MHz, CDCl3): d 0.97 (d, J = 2.4 Hz, 3H), 0.99 (d,
J = 2.3 Hz, 3H), 1.47–1.59 (m, 1H), 1.68–1.83 (m, 2H), 1.99 (s, 1H),
4.72–4.79 (m, 1H), 7.26–7.34 (m, 1H), 7.34–7.40 (m, 4H); 13C
NMR (100 MHz, CDCl3): d 22.3, 23.1, 24.8, 48.4, 72.8, 125.9,
127.5, 128.5, 145.2.
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We gratefully acknowledge financial support from the Nature
Science Foundation of Fujian Province, China (No. 2016J01086).
We also thank the Strategic Priority Research Program of the Chi-
Please cite this article in press as: Wang, Y.; et al. Tetrahedron: Asymmetry (2016), http://dx.doi.org/10.1016/j.tetasy.2016.11.011

8
Y. Wang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
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Please cite this article in press as: Wang, Y.; et al. Tetrahedron: Asymmetry (2016), http://dx.doi.org/10.1016/j.tetasy.2016.11.011