Nonenzymatic kinetic resolution of α-aryl substituted allylic alcohols catalyzed by acyl transfer catalyst Np-PIQ

Article abstract of DOI:10.1016/j.tet.2015.01.018

Chiral α-aryl substituted allylic alcohols are important versatile synthetic intermediates. We report here an effective nonenzymatic kinetic resolution of racemic α-aryl substituted allylic alcohols by introducing different aryl groups with acyl transfer

Full text of DOI:10.1016/j.tet.2015.01.018

Tetrahedron 71 (2015) 1187e1191
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Tetrahedron
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Nonenzymatic kinetic resolution of a-aryl substituted allylic
alcohols catalyzed by acyl transfer catalyst Np-PIQ
*
*
Shan-Shan Jiang, Bo-Qi Gu, Ming-Yu Zhu, Xingxin Yu , Wei-Ping Deng
Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Chiral
a
-aryl substituted allylic alcohols are important versatile synthetic intermediates. We report here
Received 7 December 2014
Received in revised form 27 December 2014
Accepted 9 January 2015
an effective nonenzymatic kinetic resolution of racemic
different aryl groups with acyl transfer catalyst Np-PIQ and propionic anhydride, providing moderate to
good selectivity factors (S¼12e37).
a-aryl substituted allylic alcohols by introducing
Available online 14 January 2015
Ó 2015 Elsevier Ltd. All rights reserved.
Keywords:
Kinetic resolution
Allylic alcohols
Nucleophilic catalyst
1. Introduction
adducts (Fig. 1). However, the nucleophilic nonenzymatic KR of a-
aryl substituted allylic alcohols has rarely been employed, and
Kinetic resolution (KR) is one of the most powerful strategies for
obtaining optically pure compounds.1 Since Vedejs,2 Fu3 and Bir-
man4 reported the pioneering work on the nonenzymatic acylative
KR of secondary alcohols, applying chiral phosphine, chiral 4-
dimethylaminopyridine (DMAP) equivalents and chiral amidine
derivatives as nucleophilic acyl transfer catalysts respectively, the
asymmetric nucleophilic acyl transfer catalysis for the KR of various
secondary alcohols has been further developed.5 Several nucleo-
philic catalysts have been designed in our group,6 such as Fc-PIP,
Np-PIQ and An-PIQ, which all showed excellent stereoselectivities
(S up to >1800) in acylative KR of arylalkyl carbinols.
the only two substrates showed the low selectivity factors of 148b
and 118c
.
Chiral allylic alcohols in optically enriched forms are useful in-
termediates, which could be transformed into different kinds of
derivatives by epoxidation, oxidation, reduction, etc.7 Much effort
has been made towards the development of excellent non-
enzymatic catalysts for the KR of sec-alcohol substrates. However,
the acylative KR of secondary allylic alcohols has received much less
attention than that of the other sec-alcohols,8 probably due to the
Fig. 1. Nucleophilic nonenzymatic acylative KR of allylic alcohols.
Herein, we would like to disclose an effective nonenzymatic KR
of a series of racemic secondary allylic alcohols with a-aryl groups
utilizing acyl transfer catalyst Np-PIQ, providing corresponding
unreacted alcohols and acylated products with moderate to good
selectivity factors (S¼12e37).
weakness of p-p stacking interaction and p-cation interaction be-
tween the carbonecarbon double bond and the acylated catalyst.
During the past decades, several kinds of substrates have been in-
vestigated, such as secondary cinnamyl alcohols, aryl alke-
nylcarbinols, polysubstituted allylic alcohols and Baylis-Hillman
2. Results and discussion
Initially, rac-1a was chosen as the model substrate to investigate
the feasibility of the asymmetric KR with different nucleophilic
catalysts (Table 1). The reaction underwent smoothly when our
newly developed catalyst Np-PIQ was used as the nucleophilic
* Corresponding authors. Tel./fax: þ86 21 64252431; e-mail addresses: xxyu@
ecust.edu.cn (X. Yu), weiping_deng@ecust.edu.cn (W.-P. Deng).
http://dx.doi.org/10.1016/j.tet.2015.01.018
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

1188
S.-S. Jiang et al. / Tetrahedron 71 (2015) 1187e1191
Table 3
Screening of anhydrides and basesa
Table 1
Screening of catalysts in kinetic resolution of secondary allylic alcoholsa
Entry
R
1a ee (%)
2a ee (%)
CHPLC (%)c
S
1
Et
Et
i-Pr
Me
Ph
78.9
72.3
33.9
30.5
4.6
81.5
81.9
78.5
70.3
21.2
49.2
46.9
30.2
30.3
17.8
23
22
12
8
2b
3
4
5
2
a
Conditions: substrate concentration 0.1 M, (EtCO)2O 0.75 equiv, DIPEA
0.75 equiv, MTBE: CHCl3 (1:1), catalyst 5 mol %.
b
Using 0.75 equiv TEA instead.
Calculated from the ee of the ester (S)-2 and unreacted alcohol (R)-1a.
c
Entry
Catalyst
t (h)
1a ee (%)
2a ee (%)
CHPLC (%)b
S
1
2
3
4
5
Fc-PIP
7.5
24
24
24
24
41.9
58.5
38.7
78.9
85.4
85.5
34.7
40.7
31.2
35.6
40.0
13
23
19
19
14
Np-PIQ
An-PIQ
(R)-BTM
Cl-PIQ
entry 5). The effect of TEA on selectivity factor of the kinetic reso-
lution was also examined, and found slightly inferior to DIPEA in
terms of both stereoselectivity and conversion (Table 3, entries 2 vs
1).
Optimization of nucleophilic catalysts, solvents, anhydrides and
bases led us to establish that 5.0 mol % Np-PIQ/(EtCO)2O
(0.75 equiv)/DIPEA (0.75 equiv)/MTBE:CHCl3(v:v¼1:1) (0.1 M)/0 ꢀC
were the optimal reaction conditions for the catalytic kinetic res-
olution. Under these conditions, the generality and scope of the
secondary allylic alcohols kinetic resolution were investigated, and
the results are summarized in Table 4.
ꢁ46.6
ꢁ84.4
52.4
78.7
a
Conditions: substrate concentration 0.1 M, (EtCO)2O 0.75 equiv, DIPEA
0.75 equiv, catalyst 5.0 mol %.
b
Calculated from the ee of the ester (S)-2a and unreacted alcohol (R)-1a.
catalyst, propionic anhydride was used as the acylative agent in
toluene at 0 ꢀC for 24 h, providing unreacted alcohol (R)-1a (58.5%
ee) and acylated product (S)-2a (85.4% ee) with the selectivity
factor S¼23 (Table 1, entry 2). Other catalysts such as Fc-PIP, An-PIQ,
(R)-BTM and Cl-PIQ displayed lower S values and activities (Table 1,
entries 1, 3e5).
Table 4
Scope and generality of the Np-PIQ catalyzed KRa
Next, solvents were screened as shown in Table 2. It revealed
that MTBE showed similar selectivity and activity to toluene (Table
2, entry 1, S¼25). Solvent CHCl3 displayed a higher activity and
a relative lower S value (Table 2, entry 4, CHPLC¼52.7%, S¼19). Then
solvent mixtures were taken into consideration (Table 2, entries
7e9), and led to the identification of MTBE/CHCl3 (v/v 1:1) as the
best choice, providing unreacted alcohol (R)-1a (78.9% ee) and ac-
ylated product (S)-2a (81.5% ee) with the selectivity factor S¼23
(Table 2, entry 7, CHPLC¼49.2%).
Entry
R1
R2
1 ee (%)
2 ee (%)
CHPLC (%)b
S
1
2
3
4
5
6
7
8
Ph
Me (1a)
Me (1b)
Me (1c)
Me (1d)
Me (1e)
Me (1f)
Me (1g)
Me (1h)
Me (1i)
Me (1j)
Me (1k)
i-Pr (1l)
78.9
77.5
50.3
24.2
63.8
63.2
50.2
73.7
82.9
71.2
48.3
26.4
81.5
88.1
86.1
84.1
87.9
83.4
86.3
81.5
72.3
85.7
75.7
88.5
49.2
46.8
36.9
22.4
42.1
43.1
36.8
47.5
53.4
45.4
39.0
23.0
23
37
22
15
30
21
22
22
16
28
12
21
p-OMePh
m-OMePh
o-OMePh
3,4-OMePh
3,4,5-OMePh
p-MePh
Table 2
Screening of solventsa
p-ClPh
9
p-NO2Ph
2-naphthyl
1-naphthyl
Ph
10
11
12c
Entry
Solvent
1a ee (%)
2a ee (%)
CHPLC (%)b
S
1
2
3
4
5
6
7
8
9
Toluene
MTBE
Et2O
CHCl3
i-Pr2O
DCM
MTBE/CHCl3 (v/v 1:1)
MTBE/Tol (v/v 1:1)
Tol/CHCl3 (v/v 1:1)
58.5
51.5
42.0
83.9
43.8
40.6
78.9
54.8
73.7
85.4
87.5
85.1
75.2
88.1
71.9
81.5
86.5
80.1
40.7
37.1
33.0
52.7
33.2
36.1
49.2
38.8
47.9
23
25
19
18
24
9
23
24
20
a
Conditions: 0.1 M of substrate concentration, 0.75 equiv (EtCO)2O, 0.75 equiv
DIPEA, 5 mol %. Np-PIQ.
b
Calculated from the ee of the ester (S)-2 and unreacted alcohol (R)-1.
Toluene as the solvent, 48 h. Absolute configuration was determined by com-
c
paring the sign of optical rotation and HPLC data with that in the literature.8c,9
The kinetic resolution of a wide array of allylic alcohols 1 with
electron-neutral, electron-deficient or electron-rich substituents
on the aromatic ring proceeded smoothly under the optimal re-
action conditions, providing moderate to good selectivity factors
(S¼12e37) (Table 4). The positions of substituents attached to the
aromatic ring had significantly effects on selectivity factors and
activities. para-Methoxyl phenyl substituted allylic alcohol 1b dis-
played higher selectivity factor and activity compare to meta- and
ortho-methoxyl phenyl substituted allylic alcohol 1c and 1d (Table
4, entries 2e4). Notably, naphthyl substituted alkenyl carbinols
were also tolerated, and 2-naphthyl substituted alkenyl carbinol 1j
a
Conditions: substrate concentration 0.1 M, (EtCO)2O 0.75 equiv, DIPEA
0.75 equiv, Np-PIQ 5.0 mol %.
b
Calculated from the ee of the ester (S)-2a and unreacted alcohol (R)-1a.
Further screening of anhydrides revealed that propionic anhy-
dride was optimal for the acylative kinetic resolution, whereas
other anhydrides displayed lower S values and activities (Table 3,
entries 1 vs 3e5). Benzoic anhydride displayed much lower selec-
tivity factor and activity compare to aliphatic anhydrides (Table 3,

S.-S. Jiang et al. / Tetrahedron 71 (2015) 1187e1191
1189
showed better selectivity and activity than 1-naphthyl substituted
alkenyl carbinol 1k, probably due to the different reinforcement of
-stacking interactions between the substrate and the acylated
4.3. The preparation of allylic alcohols10,11
p
catalyst (Table 4, entries 10, 11). Furthermore, the bulky alkyl
groups R2 resulted in lower activity even in 48 h due to the steric
hindrance (Table 4, entry 12).
Comparing with the KR of allylic alcohols without aryl groups
reported previously, better results were obtained with these sec-
ondary allylic alcohols 1, probably due to the better selectivity and
activity of our newly developed catalyst Np-PIQ and/or the syner-
gistic effect of acylated catalyst, aryl group and carbonecarbon
double bond of the substrate, which would make the interaction
between the substrate and intermediate much stronger.
To a stirred solution of phenyl-2-propanone (10 equiv) in DMF
was successively added paraformaldehyde (50 equiv), piperidine
(1.3 equiv) and AcOH (2.2 equiv). The resulting mixture was
heating at 90 ꢀC for 1 h. After cooling, water was added to the
residue and the mixture was extracted with EA. The combined
organic layers were washed with water, dried over MgSO4, fil-
tered, and concentrated to give in vacuo vinyl ketone. To a solu-
tion of vinyl ketone (1 equiv) in methanol at 0 ꢀC were added
cerium trichloride (1 equiv) and sodium borohydride (1 equiv).
The reaction mixture was stirred for 15 min at 0 ꢀC and then
saturated aqueous sodium hydrogen carbonate was added. The
mixture was extracted with diethyl ether, and the organic layer
was washed with brine, dried over sodium sulfate. After filtration
of the mixture and evaporation of the solvent, the crude product
was purified by column chromatography to afford the allylic al-
cohols 1.
3. Conclusion
In conclusion, we developed an effective nonenzymatic kinetic
resolution of racemic
a-aryl substituted allylic alcohols by in-
troducing different aryl groups with acyl transfer catalyst Np-PIQ
and propionic anhydride, and moderate to good selectivity factors
were observed (S¼12e37). Meanwhile, this protocol also provides
a complementary method for the asymmetric synthesis of sec-
ondary allylic alcohols.
4. Experimental section
4.1. General
4.3.1. 3-Phenylbut-3-en-2-ol (1a).8c Colorless oil, 85% yield; 1H
NMR (400 MHz, CDCl3):
d 7.43e7.26 (m, 5H), 5.36 (s, 1H), 5.28 (s,
1H), 4.82 (q, J¼6.3 Hz, 1H), 1.84 (s, 1H), 1.32 (d, J¼6.4 Hz, 3H). The
All reagents and starting materials were obtained commercially
and used as received unless otherwise specified. The substrates
used in the kinetic resolution experiments were prepared by Baylis-
Hillman reaction. Solvents and reagents were dried in advance.
Catalyst An-PIQ,6c Np-PIQ,6c Fc-PIP,6a (R)-BTM4c were synthesized
according to literature procedures.
ee was determined by HPLC (Chiralcel OD, 1 mL/min, 100/5
hexane/i-PrOH,
10.3 min).
l¼254 nm, retention time: (S) 8.1 min, (R)
4.3.2. 3-(4-Methoxyphenyl)but-3-en-2-ol (1b).12 Colorless oil, 87%
yield; 1H NMR (400 MHz, CDCl3):
7.41e7.33 (m, 2H), 6.94e6.85
d
1H NMR spectra were recorded on a Bruker DPX 400 MHz
spectrometer in chloroform-d3. Chemical shifts are reported in ppm
with the internal TMS signal at 0.0 ppm as a standard. The data are
reported as (s¼single, d¼doublet, t¼triple, q¼quartet, m¼multiple,
br s¼broad single, coupling constant(s) in Hertz, integration). 13C
NMR spectra were recorded on a Bruker DPX 100 MHz spectrom-
eter in chloroform-d3. Chemical shifts are reported in parts per
million with the internal chloroform signal at 77.0 ppm as
a standard.
Methods used for kinetic resolution experiments determination
of ee’s and calculation of conversions and selectivities were adopted
from previously published work.6 Enantiomeric ratios were de-
termined by HPLC, using a Diacel CHIRALCEL OD-H column and
a Diacel IF-H column with hexane and i-PrOH as eluents. Selectivity
factors and conversions were calculated from the enantiomeric
excess values of the ester products and the recovered unreacted
alcohol substrates according to Kagan’s equations.
(m, 2H), 5.31 (t, J¼1.2 Hz, 1H), 5.25 (s, 1H), 4.86e4.78 (m, 1H), 3.84
(s, 3H), 1.73 (s, 1H), 1.35 (d, J¼6.4 Hz, 3H). The ee was determined by
HPLC (Chiralcel OD, 1 mL/min, 100/5 hexane/i-PrOH,
retention time: (S) 10.1 min, (R) 11.5 min).
l¼254 nm,
4.3.3. 3-(3-Methoxyphenyl)but-3-en-2-ol (1c). Colorless oil, 91%
yield; 1H NMR (400 MHz, CDCl3):
d
7.26 (t, J¼7.9 Hz, 1H), 7.06e6.90
(m, 2H), 6.85 (dd, J¼8.3, 1.8 Hz, 1H), 5.36 (s, 1H), 5.29 (s, 1H),
4.85e4.75 (m, 1H), 3.82 (s, 3H), 1.74 (s, 1H), 1.33 (d, J¼6.4 Hz, 3H).
13C NMR (100 MHz, CDCl3):
d 159.6, 153.0, 141.5, 129.4, 119.3, 112.9,
112.8, 111.7, 69.5, 55.2, 22.6; HRMS (EI, m/z): Calcd for C11H14O2:
178.0994, found: 178.0993. The ee was determined by HPLC (Chir-
alcel OD, 1 mL/min, 90/10 hexane/i-PrOH,
time: (S) 7.9 min, (R) 11.2 min).
l¼254 nm, retention
4.3.4. 3-(2-Methoxyphenyl)but-3-en-2-ol (1d). Colorless oil, 87%
yield; 1H NMR (400 MHz, CDCl3):
7.34e7.22 (m, 1H), 7.12 (d,
d
J¼6.9 Hz, 1H), 7.01e6.83 (m, 2H), 5.46 (s, 1H), 5.08 (s, 1H), 4.69 (s,
4.2. General experimental procedure
1H), 3.84 (s, 3H), 2.53 (s, 1H), 1.23 (d, J¼6.3 Hz, 3H). 13C NMR
(100 MHz, CDCl3):
d 155.2, 151.7, 129.9, 129.0, 127.9, 119.9, 113.1,
Under nitrogen atmosphere, catalyst Np-PIQ (0.01 mmol), ra-
cemic secondary alcohol (0.2 mmol), DIPEA (0.15 mmol), MTBE
(1 mL) and CHCl3 (1 mL) were sequentially added to a 10 mL
flame-dried Schlenk tube in an ice bath. After stirring at 0 ꢀC for
5 min, the reaction mixture was treated with propionyl anhydride
(0.15 mmol). Then the resulting solution was stirred at 0 ꢀC for the
specified time and further quenched by rapid addition of metha-
nol (0.2 mL). The solution was warmed to room temperature and
stirred for an additional 2 h. The solvent was removed in vacuo,
and the residue was purified by silca gel chromatography (5%e10%
EtOAc/petroleum) to separate the ester from the unreacted
alcohol.
109.6, 69.2, 54.5, 21.3; HRMS (EI, m/z): Calcd for C11H14O2:
178.0994, found: 178.0995. The ee was determined by HPLC (Chir-
alcel OD, 1 mL/min, 90/10 hexane/i-PrOH,
time: (S) 6.2 min, (R) 9.7 min).
l¼254 nm, retention
4.3.5. 3-(3,4-Dimethoxyphenyl)but-3-en-2-ol (1e). White solid, mp
39e40 ꢀC, 86% yield; 1H NMR (400 MHz, CDCl3):
6.96 (s, 2H),
d
6.84 (d, J¼8.5 Hz, 1H), 5.31 (s, 1H), 5.24 (s, 1H), 4.80 (s, 1H), 3.90 (s,
3H), 3.89（s, 3H）, 1.73 (s, 1H), 1.34 (d, J¼6.3 Hz, 3H). 13C NMR
(100 MHz, CDCl3):
d 151.6, 147.7, 131.7, 118.1, 110.0, 109.6, 109.4,
68.6, 54.9, 21.5; HRMS (EI, m/z): Calcd for C12H16O3: 208.1099,
found: 208.1100. The ee was determined by HPLC (Chiralcel IF,

1190
S.-S. Jiang et al. / Tetrahedron 71 (2015) 1187e1191
1 mL/min, 40/1 hexane/i-PrOH,
36.4 min, (R) 39.6 min).
l¼254 nm, retention time: (S)
the ester and eeA is the enantiomeric excess of the unreacted
alcohol.
4.3.6. 3-(3,4,5-Trimethoxyphenyl)but-3-en-2-ol (1f). White solid,
mp 53e55 ꢀC, 89% yield; 1H NMR (400 MHz, CDCl3):
6.62 (s, 2H),
Acknowledgements
d
5.33 (s, 1H), 5.25 (s, 1H), 4.82e4.72 (m, 1H), 3.87 (s, 6H), 3.86 (s, 3H),
This work was supported by the Fundamental Research Funds
for the Central Universities, the National Natural Science Founda-
tion of China (No. 21372074).
1.83 (s, 1H), 1.34 (d, J¼6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d
153.1, 153.0, 137.8, 135.8, 111.5, 104.2, 102.8, 69.6, 60.9, 56.1, 22.5;
HRMS (EI, m/z): Calcd for C13H18O4: 238.1205, found: 238.1206. The
ee was determined by HPLC (Chiralcel IF, 1 mL/min, 100/5 hexane/i-
Supplementary data
PrOH,
l¼254 nm, retention time: (S) 36.0 min, (R) 32.4 min).
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2015.01.018.
4.3.7. 3-(p-Tolyl)but-3-en-2-ol (1g).13 Colorless oil, 90% yield; 1H
NMR (400 MHz, CDCl3):
d
7.29 (d, J¼8.0 Hz, 2H), 7.15 (d, J¼7.9 Hz,
2H), 5.32 (s, 1H), 5.26 (s, 1H), 4.88e4.72 (m, 1H), 2.35 (s, 3H), 1.72 (d,
J¼3.9 Hz, 1H), 1.32 (d, J¼6.4 Hz, 3H). The ee was determined by
References and notes
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l¼254 nm,
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Ohtsubo, Y.; Tsuzuki, T.; Fujimoto, T.; Yamamoto, I. Tetrahedron Lett. 2006, 47,
8227e8229; (n) Nguyen, H. V.; Motevalli, M.; Richards, C. J. Synlett 2007,
1H), 1.34 (d, J¼6.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 151.1, 147.2,
146.6, 127.8, 123.6, 115.1, 69.4, 22.6; HRMS (EI, m/z): Calcd for
C
10H11NO3: 193.0739, found: 193.0742. The ee was determined by
HPLC (Chiralcel OD, 1.0 mL/min, 40/1 hexane/i-PrOH,
retention time: (S) 16.4 min, (R) 20.8 min).
l¼254 nm,
4.3.10. 3-(Naphthalen-2-yl)but-3-en-2-ol (1j).15 White solid, mp
41e43 ꢀC, 67% yield; 1H NMR (400 MHz, CDCl3):
7.91e7.80 (m,
d
4H), 7.58 (dd, J¼8.6, 1.4 Hz, 1H), 7.55e7.46 (m, 2H), 5.50 (s, 1H), 5.45
(s, 1H), 5.01e4.92 (m, 1H), 1.83 (s, 1H), 1.41 (d, J¼6.4 Hz, 3H). The ee
was determined by HPLC (Chiralcel OD, 0.8 mL/min, 40/1 hexane/i-
€
725e728; (o) Kundig, E. P.; Carcia, A. E.; Lomberget, T.; Garcia, P. P.; Romanens,
PrOH,
l¼254 nm, retention time: (S) 17.2 min, (R) 18.9 min).
P. Chem. Commun. 2008, 3519e3521; (p) De, C. K.; Klauber, E. G.; Seidel, D. J. Am.
€
Chem. Soc. 2009, 131, 17060e17061; (q) Hrdina, R.; Muller, C. E.; Schreiner, P. R.
4.3.11. 3-(Naphthalen-1-yl)but-3-en-2-ol (1k).15 White solid, mp
Chem. Commun. 2010, 2689e2690; (r) Carbery, D. R.; Crittall, M. R.; Rzepa, H. S.
Org. Lett. 2011, 13, 1250e1253.
58e60 ꢀC, 91% yield; 1H NMR (400 MHz, CDCl3):
d
8.02 (d, J¼5.0 Hz,
6. (a) Hu, B.; Meng, M.; Wang, Z.; Du, W.; Fossey, J. S.; Hu, X.; Deng, W.-P. J. Am.
Chem. Soc. 2010, 132, 17041e17044; (b) Hu, B.; Meng, M.; Fossey, J. S.; Mo, W.;
Hu, X.; Deng, W.-P. Chem. Commun. 2011, 10632e10634; (c) Wang, Z.; Ye, J.; Wu,
R.; Liu, Y.-Z.; Fossey, J. S.; Cheng, J.; Deng, W.-P. Catal. Sci. Technol. 2014, 4,
1909e1913; (d) Jiang, S.; Hu, B.; Yu, X.; Deng, W. Chin. J. Chem. 2014, 32,
694e698.
1H), 7.86 (d, J¼4.5 Hz, 1H), 7.80 (d, J¼8.2 Hz, 1H), 7.52e7.40 (m, 3H),
7.31 (d, J¼6.9 Hz, 1H), 5.72 (s, 1H), 5.18 (s, 1H), 4.72 (s, 1H), 1.79 (s,
1H), 1.28 (d, J¼6.3 Hz, 3H). The ee was determined by HPLC (Chir-
alcel OD,1 mL/min, 40/1 hexane/i-PrOH,
(S) 9.9 min, (R) 11.2 min).
l¼254 nm, retention time:
7. (a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974e5976; (b)
Brown, J. M.; Naik, R. G. J. Chem. Soc., Chem. Commun. 1982, 348e350; (c)
Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K.
B. J. Am. Chem. Soc. 1987, 109, 5765e5780; (d) Burgess, K.; Jennings, L. D. J.
Am. Chem. Soc. 1991, 113, 6129e6139; (e) Atkinson, R. S.; Ulukanli, S.; Wil-
4.3.12. 4-Methyl-2-phenylpent-1-en-3-ol (1l).9 Colorless oil, 85%
yield; 1H NMR (400 MHz, CDCl3):
7.45e7.20 (m, 5H), 5.32 (s, 2H),
d
ꢀ
4.40 (s, 1H), 1.82e1.68 (m, 2H), 0.91 (d, J¼6.8 Hz, 3H), 0.86 (d,
liams, P. J. J. Chem. Soc., Perkin Trans. 1 1999, 2121e2128; (f) Bogar, K.; Vidal,
ꢀ
€
P. H.; Leon, A. R. A.; Backvall, J.-E. Org. Lett. 2007, 9, 3401e3404; (g) Ohmura,
T.; Takasaki, Y.; Furukawa, H.; Suginome, M. Angew. Chem., Int. Ed. 2009, 48,
2372e2375.
J¼6.8 Hz, 3H). The ee was determined by HPLC (Chiralcel OD, 1 mL/
min, 100/5 hexane/i-PrOH,
(R) 8.9 min).
l¼254 nm, retention time: (S) 5.9 min,
8. (a) Burgess, K.; Jennings, L. D. J. Am. Chem. Soc. 1990, 112, 7434e7436; (b) Bel-
lemin-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem.
Commun. 2000, 1009e1010; (c) Vedejs, E.; Mackay, J. A. Org. Lett. 2001, 3,
535e536; (d) Yamada, S.; Misono, T.; Iwai, Y.; Masumizu, A.; Akiyama, Y. J. Org.
4.4. The determination of ester’s ee value
ꢀ
ꢀ
Chem. 2006, 71, 6872e6880; (e) Dalaigh, C. O.; Connon, S. J. J. Org. Chem. 2007,
72, 7066e7069; (f) Li, X.; Jiang, H.; Uffman, E. W.; Guo, L.; Zhang, Y.; Yang, X.;
Birman, V. B. J. Org. Chem. 2012, 77, 1722e1737; (g) Hu, B.; Meng, M.; Jiang, S.;
Deng, W. Chin. J. Chem. 2012, 30, 1289e1294.
The enantiomeric excesses of the esters were determined by
hydrolysis to the parent alcohols (2 mL of 2 M KOH in methanol, at
room temperature until complete by TLC), which were analyzed as
described above.
The conversions and selectivities were calculated as CHPLC¼eeA/
(eeEþeeA), S¼ln((1-CHPLC) (1-eeA))/ln((1-CHPLC) (1þeeA)) from pre-
viously published work.6 Where eeE is the enantiomeric excess of
ꢀ
ꢀ~
ꢀ
9. García Ruano, J. L.; Fernandez-Ibanez, M. A.; Fernandez-Salas, J. A.; Maestro, M.
ꢀ
ꢀ
ꢀ
C.; Marquez-Lopez, P.; Rodríguez-Fernandez, M. M. J. Org. Chem. 2009, 74,
1200e1204.
10. (a) Campinas, U. E.; Química, I. Synth. Commun. 2003, 33, 331e340; (b) Gembus,
ꢁ
V.; Bonnet, J.; Janin, F.; Bohn, P.; Levacher, V.; Briere, J. Org. Biomol. Chem. 2010,
8, 3287e3293.

S.-S. Jiang et al. / Tetrahedron 71 (2015) 1187e1191
1191
11. Shinna, I.; Sano, Y.; Nakata, K.; Suzuki, M.; Yokoyama, T.; Sasaki, A.; Orikasa, T.;
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7599e7617.
12. Kolleth, A.; Cattoen, M.; Arseniyadis, S.; Cossy, J. Chem. Commun. 2013,
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14. Chen, F.; Tan, C. K.; Yeung, Y.-Y. J. Am. Chem. Soc. 2013, 135, 1232e1235.
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