Enantioselective Reduction of Ketones Catalyzed by Rare-Earth Metals Complexed with Phenoxy Modified Chiral Prolinols

Article abstract of DOI:10.1021/acs.joc.8b00783

Enantioselective reduction of ketones and α,β-unsaturated ketones by pinacolborane (HBpin) has been well-established by using chiral rare-earth metal catalysts with phenoxy modified prolinols. A number of highly optically active alcohols were obtained from reduction of simple ketones catalyzed by ytterbium complex 1 [L⁴Yb(L⁴H)] (H₂L⁴ = (S)-2- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol). Moreover, α,β-unsaturated ketones were selectively reduced to a wide range of chiral allylic alcohols with excellent yields, high enantioselectivity, and complete chemoselectivity, catalyzed by a single component chiral ytterbium complex 2 [L¹Yb(L¹H)] (H₂L¹ = (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol).

Full text of DOI:10.1021/acs.joc.8b00783

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Article
Enantioselective reduction of ketones catalyzed by rare-
earth metals complexed with phenoxy modified chiral prolinols
Peng Song, Chengrong Lu, Zenghui Fei, Bei Zhao, and Yingming Yao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00783 • Publication Date (Web): 10 May 2018
Downloaded from http://pubs.acs.org on May 10, 2018
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Page 1 of 9
The Journal of Organic Chemistry
mance of rare-earth metal amides combined with phenoxy-
18). It suggests that phenoxy moiety in our catalytic system is
essential, which is not only beneficial to stabilize the structure of
chiral ytterbium catalysts, but also to enhance their enantioselec-
tivity.
1
2
3
4
5
6
7
8
functionalized chiral prolinols in the stereoselective reduction of
carbonyl compounds. To our delight, a variety of simple and ,-
unsaturated ketones underwent enantioselective hydroboration
and subsequent hydrolysis, which gave optically active alcohols in
excellent yields and high to excellent enantiomeric excesses.
Since the combination of Yb[N(SiMe3)2]3 and proligand H2L4
in 1:2 molar ratio gave optimal result, we speculated that the
ytterbium complex 1 [L4Yb(L4H)] may be the active species that
catalyze the enantioselective reduction of acetophenone. This
hypothesis was consolidated by the experiment with ytterbium
complex 1, which gave the target alcohol with improved yield
(95%) and ee value (73%) (Table 1, entry 12). Thus, the routine
screening of reaction conditions, including the catalyst loading,
reaction temperature, additives, solvents and concentration, were
carried out using ytterbium complex 1 as the catalyst (SI Table
S1) and the optimal reaction conditions were established as: 10
mol % ytterbium complex 1 as the catalyst, 2 equiv. HBpin as
Results and discussion
Best to our knowledge, the utilization of efficient metal species
with chiral ligands for the purpose of stereoselective hydrobora-
tion reduction of ketones are still limited.10 In a preliminary study,
the rare-earth metal-based catalytic system, 10 mol% ytterbium
amide La[N(SiMe3)2]3 and 20 mol% phenoxy-functionalized chi-
9
10
11
12
13
14
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ral
prolinol
((S)-2,4-di-tert-butyl-6-[[2-
(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol) (H2L1)
was employed in the enantioselective reduction of a simple ketone
with 2 equivalent of borane. Results of the model reaction of ace-
tophenone are summarized in Table 1. Pinacolborane, catechol-
borane and 9-BBN were chosen to assess the influence of borane
on the reactivity and selectivity. Pinacolborane performed the best
in both reactivity and selectivity, while 9-BBN showed poor reac-
tivity, probably owing to its bulkier structure (Table 1, entries 1-
3). To investigate the effects of the central metals of catalysts on
the transformation, four homoleptic bis(trimethylsilyl)amides of
rare-earth metal amides RE[N(SiMe3)2]3 (RE = La, Yb, Nd, and
Sc) were tested, all gave about 80% yields , but different enanti-
oselectivities (Table 1, entries 3-6). Amides with central metal of
moderate ionic radius, such as Yb[N(SiMe3)2]3, gave higher ee
value (Table 1, entry 4), while the catalysts with larger metal ionic
radius (La[N(SiMe3)2]3 and Nd[N(SiMe3)2]3) or smaller one
(Sc[N(SiMe3)2]3) gave lower ee values (Table 1, entries 3, 5-6).
This may be attributed to the size of proligand H2L1 matched with
appropriate ionic radius of ytterbium, which is considered im-
portant in controlling the enantioselectivity in enantioselective
synthesis. Since the existence of LiCl in complex
[(Me3Si)2N]3RE(-Cl)Li(THF)3 may sometimes improve the ac-
o
reductant, 50 mol% pyridine as additive in DME, at -10 C for 8 h
(Table 1, entry 16).
Table 1 Screening of the reaction conditions of enantioselective
reduction of acetophenonea
Solvent
Ligand
Entry Cat.(
RE=)
Additive
T
Yield ee
(%)b (%)
(oC)
25
1d
2e
3
La
La
La
Yb
H2L1
H2L1
H2L1
H2L1
-
-
-
-
THF
THF
THF
THF
61
36
82
84
8
0
25
tivity of RE[N(SiMe3)2]3,9b, 11 or produce the opposite effect,12
a
25
28
40
chloride-bridged “ate” complex [(Me3Si)2N]3Yb(-Cl)Li(THF)3
was also tested. A dramatic decrease of ee value was observed
(Table 1, entry 7), which proved that the configuration around the
central metal plays a key role in controlling enantioselectivity. In
addition, three other phenoxy-functionalized chiral prolinols H2L2
((S)-2,6-dicumyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-
4
25
5
6
Nd
Sc
H2L1
H2L1
-
-
THF
THF
25
25
84
77
31
8
7f
Yb
Yb
H2L1
H2L2
-
-
THF
THF
25
25
85
83
9
8
12
H2L3
((S)-2-methyl-6-((2-
9
10
Yb
Yb
H2L3
H2L4
-
-
THF
THF
25
25
81
83
56
60
yl)methyl)phenol),
(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol), and H2L4
11
12
Yb
1
H2L4
-
-
-
DME
DME
25
25
84
95
68
73
((S)-2-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-
9b
yl)methyl)phenol) were also synthesized to examine the impact
of the different substituents of ligands. Higher ee values were
obtained when the substituents are bulky tert-butyl group at the
ortho- position of the phenol hydroxyl group (Table 1, entries 4,
8-10). Screening of solvents indicated that 1,2-dimethoxyethane
(DME) gave both higher yield and enantioselectivity (Table 1,
entries 10 and 11). In addition, we investigated the effects of two
more chiral ligands L5 (commercial available prolinol) and L6
(pyridyl modified prolinol) on the enantioselective reduction of
the model reaction. The yields of the corresponding alcohol were
also high, however, ee values resulted lower (Table1, entries 17-
13
14
15
16
1
1
1
1
-
-
-
-
HN(TMS)2 DME
25
25
85
75
96
90
61
75
76
81
Et3N
Py
DME
DME
DME
25
Py
-10
17
18
Yb
Yb
L5
L6
-
-
DME
DME
25
25
86
81
11
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a Reactions were performed with acetophenone (0.3 mmol) and HBpin (0.6
mmol) in 1 mL of THF for 8 h in the presence of 10 mol % catalyst and 20
mol% ligand, 0.3 equivalent of additive was added if noted. bIsolated yield.
other reaction conditions, including the catalyst loading, reaction
1
2
3
4
5
6
temperature, additives, solvents and concentration, were also car-
ried out (SI Table 2). Finally, the optimal reaction conditions were
established as: 10 mol % ytterbium complex 2 as the catalyst, 1.2
equiv. HBpin as reductant, 50 mol% pyridine as additive, in THF,
at -40 oC for 24 h (Table 3, entry 11).
e
f
cDetermined by HPLC. d Catecholborane as reductant. 9-BBN as reductant.
Complex [(Me3Si)2N]3Yb(-Cl)Li(THF)3 was used as catalyst.
A variety of different substituted acetophenones were investi-
gated under the optimal conditions. As expected, all the substrates
underwent the enantioselective reduction smoothly with catalyst 1
in DME. The data are summarized in Table 2. Substrates with
both electron-donating and electron-withdrawing groups on the
phenyl rings gave the corresponding alcohol in high yields, vary-
ing from 90-99% with, however, different ee values. Those sub-
strates bearing ortho- position substitutes gave good to excellent
ee values (up to 95%) (Table 2, 4b-4f), while other aryl methyl
ketones, substituted at meta- or para- positions resulted in re-
duced ee values (around 75%) (Table 2, 4g-4l). Diaryl ketone 3m
also smoothly gave product 4m in 90% yield and 83% ee. Hence,
we have realized the first case of rare-earth metal complex modi-
fied with phenoxy-functionalized chiral prolinols catalyzed enan-
tioselective hydroboration of simple ketones, and the results are
overall better than the previous ones,10a-b, 10d and comparable with
that of Woodward’s outcome.10c
7
8
9
A systematic study of the substrate scope, such as chalcone-
derived substrates bearing different substituent groups on both
phenyl rings, heteroaromatic, and endo-, and exo- cyclic -
unsaturated ketones, were then conducted. As seen from Table 4,
the chiral ytterbium catalyst showed high tolerance of the various
substituents. Excellent yields were observed for all the allylic
alcohols, while the ee values changed sharply.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
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40
41
42
43
44
45
46
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49
50
51
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53
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57
58
59
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Table 3 Optimization of the reaction conditions of the enantiose-
lective reduction of chalconesa
Table 2 Scope of the substituted acetophenonesa
Entry Cat.(RE=)
Ligand
H2L1
T (oC)
25
Yield (%)b
99
ee (%)c
1d
Yb
7
2
3
Yb
Y
H2L1
H2L1
H2L1
H2L1
H2L1
H2L2
H2L3
H2L4
-
25
25
25
25
25
25
25
25
25
-40
99
99
99
99
99
99
99
99
99
99
59
57
13
51
49
57
38
53
61
83
4
Sc
Sm
La
Yb
Yb
Yb
2
5
6
7
8
9
10
11e
aReactions were performed with ketone (0.3 mmol) and HBpin (0.6
mmol) in 1 mL of DME for 8 h using 10 mol % of catalyst [L4Yb(L4H)];
isolated yields; ee values were determined by HPLC.
2
-
a Reactions were performed with chalcone (0.3 mmol), HBpin (0.36 mmol)
c
in 2 mL THF. bIsolated yields. Determined by chiral HPLC analysis.
dComplex [(Me3Si)2N]3Yb(-Cl)Li(THF)3 was used as catalyst. eAddition of
Based on the good performance of Yb-catalyzed enantioselec-
tive hydroboration of simple ketones, a more intricate enantiose-
lective reduction of ,-unsaturated ketone was investigated with
reductant HBpin. A commercially available chalcone was chosed
as the substrate of the model reaction. After the composite tests of
the catalyst species and the chiral ligands, the enantioselective
hydroboration of chalcone was proved to undergo better in the
presence of ytterbium complex 2 [L1Yb(L1H)], which gave 99%
yield and 61% ee (Table 3, entry 10). The routine screenings of
50 mol% pyridine, 1 mL THF.
For noncyclic enones, containing either electron-donating
groups, such as methyl group and methoxy group, or electron-
withdrawing groups, such as halogen and nitro group, the enanti-
oselectivities of the corresponding allylic alcohols were all good,
ranging from 77% to 89% ee (Table 4, 6a-6k). Heteroaromatic
styryl ketone 6l, was also converted to corresponding allylic alco-
hol with 89% ee. However, poor enantiomeric excess of the al-
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The Journal of Organic Chemistry
performed with the standard Schlenk techniques or in the glove-
lylic alcohols from endo-, and exo- cyclic -unsaturated ketones
were observed (21-49%), although the yields are all quantitative
(Table 4, 6m-6o). The outcomes using current chiral rare-earth
metal catalysts are comparable with those of Co and Mn com-
plexes, 7a-b but slightly less than those of Ni complex system.7c
1
2
3
4
5
6
7
8
box. Solvents, such as THF, DME, toluene, hexane, and so on,
were degassed and distilled from sodium benzophenone ketyl
before use. Analytical thin layer chromatography (TLC) was per-
formed using F254 pre-coated silica gel plate (0.2 mm thickness).
After elution, plates were detected using UV radiation (254 nm)
on a UV lamp. Flash chromatography was performed using 200-
300 mesh silica gel with freshly distilled solvents. Columns were
typically packed as slurry and equilibrated with the appropriate
solvent system prior to use. Nuclear magnetic resonance spectra
were obtained on a Bruker AV-400 apparatus (CDCl3 as solvent).
Chemical shifts for NMR spectra are reported as in units of parts
per million (ppm) downfield from SiMe4 (0.0) and relative to the
signal of chloroform-d (7.26, singlet). Multiplicities were given
as: s (singlet); d (doublet); t (triplet); q (quartet); dd (doublets of
doublet); or m (multiplets). High Resolution Mass (HRMS) spec-
tra were obtained using Bruker ESI-TOF. The ee values determi-
nation was carried out using HPLC (Agilent Technologies 2000
Series) and SHIMADZU LC-20A with Daicel Chiralcel columns
Table 4 Scope of ,-unsaturated ketonesa
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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44
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58
59
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o
at 35 C. Optical rotation was measured using an Autopol IV Po-
larimeter equipped with a sodium vapor lamp at 589 nm. The
absolute configurations of 4a-4m were determined by comparing
the specific rotation with the literature data.6a-6b The absolute con-
figurations of 6a-6o were determined by comparing the specific
rotation with the literature data.4a
General procedures of the rare-earth metal amides and com-
plexes 1 and 2
Preparation of complexes RE[N(SiMe3)2]3
Complexes RE[N(SiMe3)2]3 (RE = La, Nd, Sm, Yb, Y, Sc) were
prepared according to the published procedures.13
Preparation of complex [(Me3Si)2N]3Yb(-Cl)Li(THF)3
aReactions were performed with chalcone and its derivatives (0.3 mmol),
HBpin (0.36 mmol), pyridine 0.15 mmol, 1 mL of THF at -40 °C for 24 h
in the presence of 10 mol % of complex [L1Yb(L1H)]. Isolated yields.
The ee values were determined by chiral HPLC.
Complex [(Me3Si)2N]3Yb(-Cl)Li(THF)3 was prepared according
to the published procedures.14
Preparation of complexes 1 [L4Yb(L4H)] and 2 [L1Yb(L1H)]
According to our previous work,9b to a THF solution of
Yb[N(SiMe3)2]3 (2 mmol), a THF solution of H2L1 (4 mmol)
Conclusion
(H2L1
=
(S)-2,4-di-tert-butyl-6-((2-
was
In summary, rare-earth metals complexed with phenoxy-
functionalized chiral prolinols were first explored in the enanti-
oselective hydroboration of ketones by HBpin. Enantioselective
(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol)
added and the mixture was stirred at room temperature for 12 h.
The solvent was evaporated and the mixture was crystallized in
toluene. The colorless crystals 2 were obtained at room tempera-
ture after 1 or 2 days (1.38 g, yield 62% based on ytterbium).
reduction of simple ketones were catalyzed by catalyst
1
[L4Yb(L4H)] and produced chiral alcohols with excellent yields
(90-99%) and good to excellent ee values (68-95%). Meanwhile,
using ytterbium catalyst 2 [L1Yb(L1H)], chalcone derivatives of
different substituents underwent enantioselective reduction to
form chiral allylic alcohols quantitatively with good to high enan-
tioselectivities (41-89% ee).
Using a THF solution of H2L4 (4 mmol) (H2L4 = (S)-2-tert-butyl-
6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol),
the colorless crystals 1 were obtained at room temperature after
several days (1.26 g, yield 63% based on ytterbium).
Experimental section
Typical procedure for the preparation of simple alcohols
General Procedures. All reagents are commercially availa-
ble, reagent grade, and used as received unless otherwise noted.
The reactions involving air and water sensitive components were
Typical example for the synthesis of 4a. Pyridine (0.15 mmol,
12L) was added to a stirred DME solution of the chiral ytterbi-
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The Journal of Organic Chemistry
Page 4 of 9
(minor), 15.78 min (major); HRMS (ESI, positive) m/z: [M+ Na]+
calcd. for C8H9ClONa 179.0240; found 179.0231.
um complex 1 [L4Yb(L4H)] (0.03 mmol, 33.4 mg) under argon
atmosphere. The mixture was stirred at -10 C for 30 min. Aceto-
1
o
2
3
4
5
6
7
8
9
phenone 3a (0.3 mmol, 35.1 L) was added to the mixture for
another 30 min. Pinacolborane (0.6 mmol, 87L) was added in
the above solution and stirred for 8 h at -10 C. The reaction was
quenched by 5% (V/V) TFA in ethyl acetate, and washed with
saturated solution of sodium carbonate and extracted with ethyl
acetate. The organic layer was collected and concentrated and the
crude product was purified by column chromatography (ethyl
acetate-petroleum ether, 1:5) to obtain the final hydrolysis product
4a. The enantiomeric excess of alcohol 4a was determined by
chiral HPLC.
(S)-1-(2-(Trifluoromethyl)phenyl)ethan-1-ol (4f): Colorless Oil,
(54.6 mg, yield 96%); [α]D20 = -49.29o (c 0.076, CHCl3); 1H NMR
(400 MHz, CDCl3) δ 7.55 (m, 1H, Ph), 7.28-7.40 (m, 2H, Ph),
7.12(m, 1H, Ph), 5.10(q, J = 6.28 Hz,1H, CH-OH), 3.88(s, 1H,
OH), 2.96(d, J = 6.4Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3) δ
144.7, 131.7, 128.0, 126.6, 126.2, 125.9, 125.3, 124.7, 122.8,
84.9, 24.5; 85% ee, Daicel column IA, 99% hexanes, 1% iPrOH,
1.0 mL/min, 9.36 min (minor), 11.71 min (major); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C9H9F3ONa 213.0498; found
213.0503.
o
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(S)-1-(3-Methoxyphenyl)ethan-1-ol (4g): Colorless Oil, (40.8
1
mg, yield 90%); [α]D20 = -11.66o (c 0.261, CHCl3); H NMR (400
Characteristic data of simple alcohols
MHz, CDCl3) δ 7.27 (m, 1H, Ph), 6.82-6.97 (m, 3H, Ph), 4.81(q, J
= 6.28 Hz,1H, CH-OH), 3.09(s, 1H, OH), 2.96(d, J = 6.4Hz, 3H,
CH3); 13C NMR (100 MHz, CDCl3) δ 159.6, 147.8, 129.4, 117.8,
112.6, 111.0, 69.9, 55.0, 25.2; 78% ee, HPLC: Daicel column IA,
98% hexanes, 2% iPrOH, 1.0 mL/min, 16.45 min (minor), 18.14
min (major); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C9H12O2Na 175.0730; found 175.0737.
(S)-1-Phenylethan-1-ol (4a): Colorless Oil, (32.7 mg, yield
20
90%); [α]D = -15.16o (c 0.329, CHCl3); 1H NMR (400 MHz,
CDCl3) δ 7.32 (m, 5H, Ph), 4.88 (q, J = 6.5 Hz, 1H, CH-OH),
2.11 (s, 1H, OH), 1.49 (d, J = 6.5 Hz, 3H, CH3); 13C NMR (100
MHz, CDCl3) δ 145.8, 128.5, 127.5, 125.4, 70.4, 25.2; 81% ee,
i
HPLC: Daicel column OD-H, 98% hexanes, 2% PrOH, 1.0
mL/min, 10.38 min (minor), 11.55 min (major); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C8H10ONa 145.0624; found
145.0633.
(S)-1-(3-Chlorophenyl)ethan-1-ol (4h): Colorless Oil, (42.3 mg,
yield 91%); [α]D = -64.07o (c 0.072, CHCl3); 1H NMR (400
20
MHz, CDCl3): δ 7.35 (s, 1H, Ph), 7.24(m, 3H, Ph), 4.84(q,
J=6.28, 1H, CH-OH), 2.77(s, 1H, OH), 1.45(d, J = 6.44Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 142.6, 131.0, 128.8, 127.8, 126.7,
125.9, 66.3, 23.0; 75% ee, HPLC: Daicel column OJ-H, 95%
(S)-1-(o-Tolyl)ethan-1-one (4b): Colorless Oil, (38.4 mg, yield
20
94%); [α]D = -59.65o (c 0.56, CHCl3); 1H NMR (400 MHz,
CDCl3): δ 7.50(d, J = 7.48Hz, 1H, Ph), 7.17(m, 3H, Ph), 5.11(q, J
= 6.44Hz, 1H, CH-OH), 2.33(s, 3H, Ph-CH3), 1.82( s, 1H, OH),
1.45(d, J = 6.4Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ
143.4, 133.8, 129.9, 126.7, 125.9, 124.0, 66.3, 23.4, 18.4; 94% ee,
HPLC: Daicel column IE, 99% hexanes, 1% iPrOH, 1.0 mL/min,
18.03 min (minor), 19.82 min (major); HRMS (ESI, positive) m/z:
[M+ Na]+ calcd. for C9H12ONa 159.0786; found 159.0793.
i
hexanes, 5% PrOH, 1.0 mL/min, 9.12 min (major), 10.39 min
(minor); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C8H9ClONa 179.0240; found 179.0246.
(S)-1-(4-Chlorophenyl)ethan-1-one (4i): Colorless Oil, (43.8 mg,
20
yield 94%); [α]D = -21.23o (c 0.529, CHCl3); 1H NMR (400
MHz, CDCl3): δ 7.29(m, 4H, Ph), 7.80(q, J = 6.36Hz, CH-OH),
3.58(br, 1H, OH), 1.44(d, J = 6.48Hz, 3H, CH3); 13C NMR (100
MHz, CDCl3): δ 143.8, 132.4, 128.0, 126.4, 69.0, 24.7; 77% ee,
(S)-1-(2,6-Dimethylphenyl)ethan-1-ol (4c)：white solid, mp 64-
o
20
66 C (40.5 mg, yield 90%); [α]D = -54.7o (c 0.11, CHCl3);1H
NMR (400 MHz, CDCl3) δ 7.01-7.10 (m, 3H, Ph), 5.39(q, J =
6.28 Hz,1H, CH-OH), 2.48(s, 6H, CH3-Ph), 2.10(s, 1H, OH),
1.55(d, J = 6.4Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3) δ
140.1, 135.1, 128.9, 126.4, 87.1, 20.9, 20.2; 90% ee, HPLC:
i
HPLC: Daicel column OD-H, 99% hexanes, 1% PrOH, 1.0
mL/min, 14.71 min (minor), 15.22 min (major); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C8H9ClONa 179.0240; found
179.0233.
i
Daicel column OD-H, 99% hexanes, 1% PrOH, 1.0 mL/min,
11.48 min (major), 14.02 min (minor); HRMS (ESI, positive) m/z:
(S)-1-(4-Bromophenyl)ethan-1-one (4j): Colorless Oil, (57.5 mg,
[M+ Na]+ calcd. for C10H14ONa 173.0937; found 173.0935
1
yield 96%); H NMR (400 MHz, CDCl3): δ 7.41 (d, J = 8.44 Hz,
2H, Ph), 7.13 (d, J = 8.40 Hz, 2H, Ph), 4.70 (q, J = 6.08 Hz, 1H,
CH-OH), 4.0 (s, 1H, OH), 1.37 (d, J = 6.56 Hz, 3H, CH3); 13C
NMR (100 MHz, CDCl3): δ 144.3, 130.9, 126., 120.5, 68.9, 24.7;
72% ee, HPLC: Daicel column OD-H, 98% hexanes, 2% iPrOH,
1.0 mL/min, 12.46 min (minor), 13.21 min (major); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C8H9BrONa 222.9729; found
222.9723.
(S)-1-(2-methoxyphenyl)ethan-1-ol (4d): Colorless Oil, (41.7
20
1
mg, yield 92%); [α]D = -52.08o (c 0.63, CHCl3); H NMR (400
MHz, CDCl3) δ 7.28-7.45 (m, 2H, Ph), 6.93-7.04 (m, 2H, Ph),
5.17(q, J = 6.32 Hz,1H, CH-OH), 3.88 (s, 1H, OH), 3.19 (s, 3H,
OCH3), 1.55(d, J = 6.4Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
155.9, 133.3, 127.6, 125.6, 120.3, 109.9, 85.4, 54.7, 22.8; 95% ee,
i
HPLC: Daicel column OD-H, 98% hexanes, 2% PrOH, 1.0
(S)-1-(4-Nitrophenyl)ethan-1-one (4k): Yellow Oil, (49.5mg,
yield 99%); [α]D20 = -22.83o (c 0.46, CHCl3); 1H NMR (400 MHz,
CDCl3): δ 8.06(d, J = 8.8Hz, 2H, Ph), 7.44(d, J = 8.8Hz, 2H, Ph),
4.92(q, J = 6.28Hz, 1H, CH-OH), 2.65(br, 1H, OH), 1.41(d, J =
6.52Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ 152.9, 146.4,
125.6, 123.1, 68.7, 24.8; 76% ee, HPLC: Daicel column IA, 98%
hexanes, 2% iPrOH, 1.0 mL/min, 16.77 min (minor), 17.18 min
(major); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C8H9NO3Na 190.0480; found 190.0471.
mL/min, 11.53 min (minor), 12.16 min (major); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C9H12O2Na 175.0730; found
175.0335.
(S)-1-(2-Chlorophenyl)ethan-1-ol (4e): Colorless Oil, (42.6 mg,
20
yield 92%); [α]D = -27.45o (c 0.255, CHCl3); 1H NMR (400
MHz, CDCl3): δ 7.57 (d, J = 2.96Hz, 1H, Ph), 7.31 (m, 2H, Ph),
7.18 (m, 1H, Ph), 5.26(q, 1H, CH-OH), 3.28(br, 1H, OH), 1.46(d,
J = 6.42, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ 142.6, 131.0,
128.3, 127.8, 126.7, 125.9, 66.3, 23.0; 90% ee, HPLC: Daicel
column OD-H, 99% hexanes, 1% iPrOH, 0.8 mL/min, 15.13 min
(S)-1-(p-Tolyl)ethan-1-one (4l): Colorless Oil, (37.5 mg, yield
20
92%); [α]D = -39.47o (c 0.14, CHCl3); 1H NMR (400 MHz,
CDCl3): δ 7.26(m, 4H, Ph), 4.85(q, J = 6.36Hz, 1H, CH-OH),
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The Journal of Organic Chemistry
2.41(s, 3H, Ph-CH3), 1.5(d, J =7.2Hz, 3H, CH3); 13C NMR (100
(100 MHz, CDCl3): δ 159.9, 142.9, 141.2, 138.1, 132.0, 130.5,
129.7, 128.7, 127.9, 127.2, 126.5, 119.5, 113.6, 111.9, 75.1, 55.3;
83% ee, HPLC: OD-H, 90% hexanes, 10% iPrOH, 1.0 mL/min,
9.7 min (major), 10.6 min (minor); HRMS (ESI, positive) m/z:
[M+ Na]+ calcd. for C16H16O2Na 263.1048; found 263.1052.
1
2
3
4
MHz, CDCl3): δ 142.7, 136.3, 128.6, 125.0, 69.5, 24.7, 20.7; 68%
i
ee, HPLC: Daicel column OJ-H, 95% hexanes, 5% PrOH, 1.0
mL/min, 11.14 min (major), 13.07 min (minor); HRMS (ESI,
positive) m/z: [M+ Na]+ calcd. for C9H12ONa 159.0786; found
159.0783.
5
6
7
8
(S, E)-1-Phenyl-3-(p-tolyl)prop-2-en-1-ol (6d): Colorless Oil,
(66.6 mg, yield 99%); [α]D20 = -23o (c 0.2, CHCl3); 1H NMR (400
MHz, CDCl3): δ 7.44 (m, 2H, Ph), 7.39 (m, 2H, Ph), 7.29 (m, 3H,
Ph), 7.12 (m, 2H, Ph), 6.64 (d, J = 15.84 Hz, 1H, CH=CH), 6.36
(dd, J1 = 15.84 Hz, J2 = 6.60 Hz, 1H, CH=CH), 5.37 (d, J = 6.54
Hz, 1H, CH), 2.35 (s, 3H, CH3), 2.16 (s, 1H, OH); 13C NMR (100
MHz, CDCl3): δ 141.6, 138.4, 137.7, 137.5, 136.9, 134.0, 131.6,
131.4, 130.7, 129.4, 128.6, 127.7, 127.2, 126.7, 75.4, 21.4; 79%
o
(S)-Phenyl-(o-tolyl)methanol (4m)：White solid, mp 88-90 C,
(53.4 mg, yield 90%); [α]D = -12.7o (c 0.68, CHCl3); H NMR
(400 MHz, CDCl3) δ 7.54-7.56 (m, 2H, Ph), 7.17-7.36(m, 6H, Ph),
6.02(s, 1H, CH-OH ), 2.30(s, 1H, OH), 2.28(s, 3H, CH3); 13C
NMR (100 MHz, CDCl3) δ 142.4, 141.0, 134.9, 130.1, 128.0,
127.1, 127.0, 126.7,125.8, 125.6, 72.8, 18.9; 83% ee, HPLC:
Daicel column OJ-H, 95% hexanes, 5% iPrOH, 1.0 mL/min, 22.42
min (major), 23.73 min (minor); HRMS (ESI, positive) m/z: [M+
Na]+ calcd. for C14H14ONa 221.0937; found 221.0945.
20
1
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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36
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44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
i
ee, HPLC: OD-H, 90% hexanes, 10% PrOH, 1.0 mL/min, 10.0
min (minor), 12.7 min (major); HRMS (ESI, positive) m/z: [M+
Na]+ calcd. for C16H16ONa 247.1099; found 247.1108.
(S, E)-3-(4-Fluorophenyl)-1-phenylprop-2-en-1-ol (6e): White
Typical procedure for the preparation of allylic alcohols
20
solid, mp 68-70 oC, (68 mg, yield 99%); [α]D = +16o (c 0.3,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.25 (m, 4H, Ph), 7.20
Typical example for the synthesis of 6a. Pyridine (0.15 mmol,
12 L) was added to a stirred THF solution of the chiral ytterbium
complex 2 [L1Yb(L1H)] (0.03 mmol, 33.4 mg) under argon at-
(m, 2H, Ph), 7.14 (m, 1H, Ph), 6.93 (m, 2H, Ph), 6.52 (d, J =
15.84 Hz, 1H, CH=CH), 6.24 (dd, J1 = 15.84 Hz, J2 = 6.56 Hz,
1H, CH=CH), 5.24 (d, J = 6.52 Hz, 1H, CH), 2.18 (s, 1H, OH);
13C NMR (100 MHz, CDCl3): δ 161.2, 136.5, 131.9, 131.5, 130.9,
130.0, 128.8, 128.2, 128.1, 127.2, 127.2, 126.8, 115.7, 115.5,
o
mosphere. The mixture was stirred at -40 C for 30 min. Then,
pinacolborane (0.36 mmol, 52 L) was added in the above solu-
tion for another 30 min. Chalcone 5a (0.3 mmol, 58.3 L) was
added to the mixture and stirred for further 24 h. The reaction was
quenched with water, some silica-gel powder was added to organ-
ic phase, which was concentrated to dry. The crude product was
purified by column chromatography (ethyl acetate-petroleum
ether, 1:10) to obtain the final hydrolysis product 6a. The enanti-
omeric excess of allylic alcohol 6a was determined by chiral
HPLC.
i
74.6; 79% ee, HPLC: OD-H, 90% hexanes, 10% PrOH, 1.0
mL/min, 12.2 min (major), 17.4 min (minor); HRMS (ESI, posi-
tive) m/z: [M+ Na]+ calcd. for C15H13FONa 251.0848; found
251.0858.
(S, E)-3-(4-Chlorophenyl)-1-phenylprop-2-en-1-ol (6f): White
20
Solid, mp 72-74 oC, (73 mg, yield 99%); [α]D = -25o (c 0.2,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.30 (m, 4H, Ph), 7.19
(m, 5H, Ph), 6.52 (d, J = 15.88 Hz, 1H, CH=CH), 6.27 (dd, J1 =
15.84 Hz, J2 = 6.32 Hz, 1H, CH=CH), 5.26 (d, J = 6.24 Hz, 1H,
CH), 2.10 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 141.0,
139.8, 135.2, 133.6, 132.3, 131.1, 130.0, 128.89, 128.82, 128.5,
128.0, 127.2, 126.8, 126.5, 75.1; 81% ee, HPLC: OD-H, 90%
Characteristic data of allylic alcohols
(S,E)-1,3-Diphenylprop-2-en-1-ol (6a): White Solid, mp 56-58
oC, (62.8 mg, yield 99%); [α]D = -20o (c 0.4, CHCl3); H NMR
(400 MHz, CDCl3): δ 7.31 (m, 6H, Ph), 7.22 (m, 3H, Ph), 7.15
(m, 1H, Ph), 6.61 (d, 1H, J = 15.84 Hz , CH=CH), 6.31 (dd, J1 =
15.84 Hz, J2 = 6.60 Hz,1H, CH=CH), 5.30 (d, J = 6.36 Hz, 1H,
CH), 2.04 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 142.9,
136.7, 131.7, 130.7, 126.8, 128.7, 128.0, 127.9, 126.8, 126.5. 83%
20
1
i
hexanes, 10% PrOH, 1.0 mL/min, 10.9 min (minor), 14.4 min
(major); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C15H13ClONa 267.0553; found 267.0558.
(S, E)-3-(4-Nitrophenyl)-1-phenylprop-2-en-1-ol (6g): Yellow
i
20
1
Oil, (76 mg, yield 99%); [α]D = -41o (c 0.3, CHCl3); H NMR
(400 MHz, CDCl3): δ 8.16 (m, 2H, Ph), 7.50 (m, 2H, Ph), 7.41
(m, 4H, Ph), 7.25 (m, 1H, Ph), 6.79 (d, J = 15.88 Hz, 1H,
CH=CH), 6.56 (dd, J1 = 15.88 Hz, J2 = 5.76 Hz, 1H, CH=CH),
5.43 (d, J = 5.68 Hz, 1H, CH), 2.19 (s, 1H, OH); 13C NMR (100
MHz, CDCl3): δ 147.0, 143.3, 142.2, 136.4, 135.0, 129.0, 128.9,
128.5, 128.3, 127.9, 127.4, 127.2, 126.5, 124.0, 74.6; 77% ee,
HPLC: OD-H, 90% hexanes, 10% iPrOH, 1.0 mL/min, 21.6 min
(minor), 23.1 min (major); HRMS (ESI, positive) m/z: [M+Na]+
calcd. for C15H13NO3Na 278.0793; found 278.0792.
ee, HPLC: OD-H, 90% hexanes, 10% PrOH, 1.0 mL/min, 13.4
min (major), 16.8 min (minor); HRMS (ESI, positive) m/z:
[M+Na]+ calcd. for C15H14ONa 233.0942; found 233.0946.
(S,E)-3-(4-Methoxyphenyl)-1-phenylprop-2-en-1-ol(6b): Color-
20
1
less Oil, (71.7 mg, yield 99%); [α]D = -11o (c 0.4, CHCl3); H
NMR (400 MHz, CDCl3): δ 7.44 (m, 2H, Ph), 7.32 (m, 5H, Ph),
6.87 (m, 2H, Ph), 6.61 (m, 1H, CH=CH), 6.23 (m, 1H, CH=CH),
5.37 (d, J = 6.72 Hz, 0.5H, CH), 5.09 (m, 0.5H, CH), 3.81 (m, 3H,
CH3), 1.86 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 159.3,
136.9, 133.5, 130.9, 129.6, 128.6, 128.5, 128.0, 127.8, 127.7,
127.2, 127.2, 128.7, 114.1, 78.8, 55.4; 83% ee, HPLC: OD-H,
90% hexanes, 10% iPrOH, 1.0 mL/min, 15.1 min (minor), 17.1
min (major); HRMS (ESI, positive) m/z: [M+Na]+ calcd. for
C16H16O2Na 263.1048; found 263.1047.
(S, E)-1-(4-Chlorophenyl)-3-phenylprop-2-en-1-ol (6h): White
20
Solid, mp 64-66 oC, (72.8 mg, yield 99%); [α]D = -8o (c 0.2,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.23 (m, 8H, Ph), 7.16
(m, 1H, Ph), 6.52 (d, J = 15.84 Hz, 1H, CH=CH), 6.22 (dd, J1 =
15.80 Hz, J2 = 6.64 Hz, 1H, CH=CH), 5.21 (d, J = 6.64 Hz, 1H,
CH), 2.27 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 141.3,
136.4, 133.6, 132.2, 131.2, 130.2, 128.9, 128.88, 128.81, 128.5,
128.1, 128.0, 127.8, 126.8, 74.6; 82% ee, HPLC: OD-H, 90%
(S, E)-3-(2-Methoxyphenyl)-1-phenylprop-2-en-1-ol (6c): Col-
20
1
orless Oil, (72 mg, yield 99%); [α]D = -11o (c 0.4, CHCl3); H
NMR (400 MHz, CDCl3): δ 7.32 (m, 2H, Ph), 7.22 (m, 2H, Ph),
7.20 (m, 1H, Ph), 7.12 (m, 1H, Ph), 6.89 (m, 1H, Ph), 6.82 (m,
1H, Ph), 6.71 (m, 1H, Ph), 6.54 (d, J = 15.80 Hz, 1H, CH=CH),
6.25 (dd, J1 = 15.80 Hz, J2 = 6.68 Hz, 1H, CH=CH), 5.26 (d, J =
6.44 Hz, 1H, CH), 3.69 (s, 3H, CH3), 2.12 (s, 1H, OH); 13C NMR
i
hexanes, 10% PrOH, 1.0 mL/min, 13.4 min (major), 19.0 min
(minor); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C15H13ClONa 267.0553; found 267.0558.
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Page 6 of 9
(S, E)-1-(4-Bromophenyl)-3-phenylprop-2-en-1-ol (6i): White
127.0, 126.3, 125.1, 124.9, 78.5, 35.7, 21.4; 49% ee, HPLC: OD-
H, 90% hexanes, 10% iPrOH, 1.0 mL/min, 7.8 min (major), 9.1
min (minor); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C17H16ONa 259.1099; found 259.1104.
20
1
2
3
4
5
6
7
8
Soild, mp 68-70 oC, (86 mg, yield 99%); [α]D = -10o (c 0.2,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.39 (m, 2H, Ph), 7.22
(m, 7H, Ph), 6.59 (d, J = 15.80 Hz, 1H, CH=CH), 6.21 (dd, J1 =
15.80 Hz, J2 = 6.64 Hz, 1H, CH=CH), 5.25 (d, J = 6.48 Hz, 1H,
CH), 2.11 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 141.8,
136.3, 132.2, 131.9, 131.8, 131.2, 130.3, 129.6, 128.9, 128.8,
128.3, 128.2, 126.8, 121.7, 74.6; 83% ee, HPLC: OD-H, 90%
(R, E)-2-(4-Fluorobenzylidene)-1,2,3,4-tetrahydronaphthalen-
1-ol (6o): Yellow Oil, (69.7 mg, yield 99%); [α]D20 = +12o (c 0.2,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.44 (m, 1H, Ph), 7.22
i
(m, 4H, Ph), 7.14 (m, 1H, Ph), 6.99 (m, 2H, Ph), 6.67 (s, 1H,
CH=CH), 5.15 (s, 1H, CH), 2.98 (s, 1H, CH2), 2.74 (m, 3H, CH2),
2.12 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 162.9, 140.9,
138.8, 137.4, 133.4, 130.5, 130.4, 128.4, 128.0, 127.8, 126.7,
124.4, 115.4, 115.2, 73.9, 29.8, 24.2; 21% ee, HPLC: AD-H, 90%
hexanes, 10% PrOH, 1.0 mL/min, 14.2 min (major), 20.3 min
(minor); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C15H13BrONa 311.0047; found 311.0056.
9
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14
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16
17
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28
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35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(S,
E)-1-(4-Methoxyphenyl)-3-phenylprop-2-en-1-ol
(6j):
o
20
i
White Solid, mp 103-105 C, (71.6 mg, yield 99%); [α]D = -10o
hexanes, 10% PrOH, 1.0 mL/min, 20.8 min (major), 23.0 min
1
(c 0.2, CHCl3); H NMR (400 MHz, CDCl3): δ 7.39 (m, 7H, Ph),
(minor); HRMS (ESI, positive) m/z: [M+Na]+ calcd. for
C17H15FONa 277.1005; found 277.1010.
6.93 (m, 2H, Ph), 6.56 (m, 1H, CH=CH), 6.22 (m, 1H, CH=CH),
5.04 (m, 1H, CH), 3.80 (m, 3H, CH3), 1.29 (s, 1H, OH); 13C NMR
(100 MHz, CDCl3): δ 137.6, 133.8, 131.4, 131.3, 130.6, 130.5,
129.2, 128.5, 127.6, 127.1, 127.0, 126.6, 126.5, 126.3, 75.2, 21.1;
81% ee, HPLC: OD-H, 90% hexanes, 10% iPrOH, 1.0 mL/min,
17.5 min (major), 23.5 min (minor); HRMS (ESI, positive) m/z:
[M+ Na]+ calcd. for C16H16O2Na 263.1048; found 263.1045.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Tables of screening of the reaction conditions, NMR and HPLC
spectra of compounds
(S, E)-3-(4-Isopropylphenyl)-1-(p-tolyl)prop-2-en-1-ol (6k):
White Solid, mp 77-79 oC, (79.2 mg, yield 99%); [α]D20 = +20o (c
0.2, CHCl3); H NMR (400 MHz, CDCl3): δ 7.33 (m, 5H, Ph),
1
AUTHOR INFORMATION
7.20 (m, 4H, Ph), 6.69 (d, J = 15.84 Hz, 1H, CH=CH), 6.34 (dd,
J1 = 15.80 Hz, J2 = 6.48 Hz, 1H, CH=CH), 5.34 (d, J = 6.40 Hz,
1H, CH), 2.91 (s, 1H, CH), 2.37 (s, 3H, CH3), 2.12 (s, 1H, OH),
1.26 (m, 6H, CH3); 13C NMR (100 MHz, CDCl3): δ 148.7, 138.9,
138.6, 137.6, 137.3, 134.5, 134.1, 131.3, 129.9, 129.3, 127.2,
127.2, 126.7, 126.7, 79.1, 34.0, 24.1, 21.3; 87% ee, HPLC: OD-H,
90% hexanes, 10% iPrOH, 1.0 mL/min, 8.9 min (minor), 9.8 min
(major); HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for
C19H22ONa 289.1568; found 289.1570.
Corresponding Author
* Fax: +86-512-65880305; Tel: +86-512-65880305; Email ：
zhaobei@suda.edu.cn, yaoym@suda.edu.cn
ORCID
Bei Zhao: 0000-0001-8687-2632
Yingming Yao: 0000-0001-9841-3169
ACKNOWLEDGMENT
(S, E)-3-Phenyl-1-(thiophen-2-yl)prop-2-en-1-ol (6l): White
o
20
Solid, mp 50-52 C, (63.7 mg, yield 99%); [α]D = -20o (c 0.2,
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Grant No. 21572151) and
PAPD.
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.32 (m, 2H, Ph), 7.23
(m, 2H, Ph), 7.15 (m, 1H, Ph), 6.94 (m, 1H, Ph), 6.90 (m, 1H, Ph),
6.61 (d, J = 15.80 Hz, 1H, CH=CH), 6.34 (dd, J1 = 15.76 Hz, J2 =
6.48 Hz, 1H, CH=CH), 5.51 (d, J = 6.36 Hz, 1H, CH), 2.25 (s,
1H, OH); 13C NMR (100 MHz, CDCl3): δ 145.0, 141.9, 136.4,
132.6, 129.1, 128.8, 128.1, 127.4, 126.9, 126.3, 125.8, 125.3,
REFERENCES
(a) Farina, V.; Reeves, J. T.; Senanayake, C. H.; Song, J. J.
Asymmetric Synthesis of Active Pharmaceutical Ingredients.
Chem. Rev. 2006, 106, 2734-2793. (b) Klingler, F. D. Asymmetric
Hydrogenation of Prochiral Amino Alcohols for Pharmaceutical
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i
75.4; 89% ee, HPLC: OD-H, 90% hexanes, 10% PrOH, 1.0
mL/min, 10.9 min (major), 14.4 min (minor); HRMS (ESI, posi-
tive) m/z: [M+ Na]+ calcd. for C13H12OSNa 239.0507; found
239.0518.
(R)-3,4,5,6-Tetrahydro-[1,1'-biphenyl]-3-ol (6m): White Solid,
mp 52-54 oC, (52 mg, yield 99%); [α]D20 = +6o (c 0.2, CHCl3); 1H
NMR (400 MHz, CDCl3): δ 7.39 (m, 2H, Ph), 7.31 (m, 2H, Ph),
7.25 (m, 1H, Ph), 6.12 (m, 1H, CH=CH), 4.38 (m, 1H, CH), 2.37
(m, 2H, CH2, OH), 1.92 (m, 2H, CH2), 1.71 (m, 3H, CH2) ; 13C
NMR (100 MHz, CDCl3): δ 141.5, 140.2, 128.4, 127.6, 126.7,
125.5, 66.5, 31.8, 27.6, 19.6; 41% ee, HPLC: OD-H, 90% hex-
anes, 10% iPrOH, 1.0 mL/min, 7.6 min (minor), 15.5 min (major);
HRMS (ESI, positive) m/z: [M+ Na]+ calcd. for C12H14ONa
197.0942; found 197.0951.
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20
(6n): Colorless Oil, (70 mg, yield 99%); [α]D = +16o (c = 0.2,
1
CHCl3); H NMR (400 MHz, CDCl3): δ 7.49 (m, 1H, Ph), 7.26
(m, 5H, Ph), 7.16 (m, 2H, Ph), 6.80 (m, 1H, CH=CH), 5.75 (m,
1H, CH), 3.92 (m, 1H, CH2), 3.77 (m, 1H, CH2), 2.35 (s, 3H,
CH3), 2.06 (s, 1H, OH); 13C NMR (100 MHz, CDCl3): δ 143.8,
143.3, 141.2, 137.0, 134.5, 129.3, 129.2, 128.9, 128.7, 127.3,
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The Journal of Organic Chemistry
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