Kinetic resolution of sterically hindered secondary alcohols catalyzed by aminophosphinite organocatalyst

Article abstract of DOI:10.1016/j.tet.2017.11.062

Kinetic resolution of secondary alcohols by benzoylation using a phosphinite derivative of (1S,2R)-1-amino-2-indanol as the catalyst was investigated. The aminophosphinite catalyst is effective for the kinetic resolution of aryl cycloalkyl carbinols with a small number of examples for organocatalytic kinetic resolution to achieve resolution with s = up to 44. Although the benzoylation of phenylalkanols proceeded with a low selectivity, 1-arylalkanols bearing at least one substituent at the ortho position on the benzene ring or a branched alkyl group on the carbinol carbon were resolved with acceptable selectivity.

Full text of DOI:10.1016/j.tet.2017.11.062

Tetrahedron 74 (2018) 296e302
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Kinetic resolution of sterically hindered secondary alcohols catalyzed
by aminophosphinite organocatalyst
Nanami Hara, Shu Fujisawa, Mizuki Fujita, Mikako Miyazawa, Kazuma Ochiai,
Satoshi Katsuda, Tetsuya Fujimoto*
Course of Applied Molecular Chemistry, Division of Chemistry and Materials, Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano,
386-8567, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 July 2017
Received in revised form
18 November 2017
Accepted 21 November 2017
Available online 23 November 2017
Kinetic resolution of secondary alcohols by benzoylation using a phosphinite derivative of (1S,2R)-1-
amino-2-indanol as the catalyst was investigated. The aminophosphinite catalyst is effective for the
kinetic resolution of aryl cycloalkyl carbinols with a small number of examples for organocatalytic kinetic
resolution to achieve resolution with s ¼ up to 44. Although the benzoylation of phenylalkanols pro-
ceeded with a low selectivity, 1-arylalkanols bearing at least one substituent at the ortho position on the
benzene ring or a branched alkyl group on the carbinol carbon were resolved with acceptable selectivity.
© 2017 Elsevier Ltd. All rights reserved.
Keywords:
Kinetic resolution
Secondary alcohol
Benzoylation
Organocatalysis
1. Introduction
resolution6c,12; to the best of our knowledge, successful acylative
kinetic resolution of these substrates by nonenzymatic organo-
Kinetic resolution of racemic alcohols is a powerful methodol-
ogy for obtaining chiral alcohols or their derivatives, versatile
synthetic building blocks for organic synthesis. Especially, nonen-
zymatic acyl transfer organocatalysts are used to achieve kinetic
resolution through the concise esterification of alcohols; therefore,
the development of more reactive and stereoselective organo-
catalysts has been performed in the last two decades.1 Most of them
are nucleophilic chiral organocatalysts that activate acylating re-
agents, and many successful examples using diverse chiral cata-
lysts, e.g., diamine,2 N,N-dimethylaminopyridine (DMAP),3
imidazole,4 phosphane,5 N-heterocyclic carbene derivatives,6
amidine-based catalysts,7 and synthetic peptides,8 have been re-
ported. Most of these catalysts have been mainly used in the kinetic
resolution of racemic secondary alcohols such as aryl alkyl carbi-
nols,1,9 and allylic10 or propargylic11 alcohols to evaluate their cat-
alytic potential. Especially, aryl alkyl carbinols have been used as
the most common substrates from the early stage of exploration of
acylative kinetic resolution using organocatalysts. In contrast, aryl
cycloalkyl carbinols are still rare substrates for the relevant kinetic
catalysts has not been reported.
We have been studying the nucleophilic chiral acylative orga-
nocatalysts and demonstrated that the phosphinite derivatives of
cinchona alkaloids 1a,b or an aminoindanol 2 are effective catalysts
for the asymmetric desymmetrization13 or kinetic resolution14 of
diols (Fig. 1). Especially, the phosphinite derivatives of an amino-
indanol are more practical small-molecule catalysts than cinchona
alkaloid derivatives in terms of catalytic activity, air stability, and
commercial availability of both the enantiomers of (1S*,2R*)-ami-
noindanol. To clarify the applicability of the catalyst to the kinetic
resolution of racemic monools, diverse secondary alcohols were
subjected to kinetic resolution catalyzed by aminoindanol phos-
phinite derivative 2. The catalyst was found to be more effective for
the kinetic resolution of aryl cycloalkyl carbinols than aryl acyclic
alkyl carbinols such as 1-phenylethanol. Herein, we report the
unique substrate specificity of the catalyst, affected by the substi-
tution mode around the carbinol carbon atom of the substrates.
2. Results and discussion
To use aminoindanol-derived phosphinite 2 in the kinetic res-
olution of monools, asymmetric benzoylation reaction was inves-
tigated using benzylic alcohol derivatives as the substrates. Among
* Corresponding author.
E-mail address: tfujimo@shinshu-u.ac.jp (T. Fujimoto).
https://doi.org/10.1016/j.tet.2017.11.062
0040-4020/© 2017 Elsevier Ltd. All rights reserved.

N. Hara et al. / Tetrahedron 74 (2018) 296e302
297
the selectivity factor for cyclopropyl carbinol apparently
decreased (s ¼ 2.7) and the configuration of the predominantly
recovered alcohol was R. These results indicated that the size of
cycloalkyl group affected the resolving efficiency and stereo-
chemical outcome for the kinetic resolution catalyzed by 2. The
carbinols having heteroaromatic rings (rac-3eeh) were also
subjected to the similar kinetic resolution. Pyridin-2-yl carbinol
rac-3e was resolved with an excellent s value (s ¼ 44). In contrast,
for the reaction of the isomer, pyridine-3-yl carbinol rac-3f, the
racemic benzoate and unreacted alcohol were obtained. Presum-
ably, the pyridine moiety in the substrate rac-3f seemed to act as a
Lewis base activating benzoyl chloride before the non-
stereoselective reaction proceeded. On the other hand, the
nucleophilicity of the nitrogen atom in pyridin-2-yl carbinol rac-
3e was thought to be decreased, because of steric repulsion by a
bulky substituent at 2-position or intramolecular hydrogen
bonding with a hydroxyl group. As a result, the reaction of rac-3e
was assumed to occur without background reaction promoted by
the pyridine moiety in the carbinol. The reaction of carbinols
having a five-membered heteroaromatic ring (rac-3geh) was also
carried out. The reaction of these substrates proceeded with a
good selectivity and the recovered alcohols having S configuration
similar to that of rac-3a.
The kinetic resolution of aryl acyclic alkyl carbinols rac-5ael
containing diverse substituents around the carbinol carbons was
also performed to investigate the substrate scope of the acylative
kinetic resolution catalyzed by 2 (Scheme 2). First, 1-phenylethanol
derivatives rac-5aee with an electronically different substituent at
the para position on the benzene ring were used for the kinetic
resolution. When substrates with an electron-withdrawing group
such as chloro and trifluoromethyl groups (rac-5d, 5e) were used,
the selectivity factors slightly increased compared to the other
substrates. However, all these substrates were resolved with a
lower selectivity than the cycloalkyl carbinols. In contrast to
cycloalkyl carbinols, the R isomers of alcohols were preferentially
recovered. A similar secondary alcohol with a naphthalene ring
(rac-5f) in place of benzene ring was not effective as well.
Fig. 1. Aminophosphinite catalysts for asymmetric acylation of diols.
these substrates, cyclohexyl(phenyl)methanol rac-3a was a prom-
ising substrate for the kinetic resolution catalyzed by 2. The reac-
tion of rac-3a with benzoyl chloride in the presence of 10 mol% of 2
in CHCl3 proceeded with good selectivity (s ¼ 25, Table 1, entry 1).
Although similar reactions using acetonitrile as the solvent affor-
ded unreacted alcohol 3a and benzoate 4a with a lower enantio-
selectivity (entry 2), the reactions in CH2Cl2 or 1,2-dichloroethane
proceeded with a comparable selectivity to that in CHCl3 (entries
3 and 4). On the other hand, the reaction in a less polar solvent,
toluene, was very sluggish, providing the benzoate in a low yield
under the same reaction conditions (entry 5). Similar reaction un-
der a reduced catalyst loading (5 mol%, entry 6) in CHCl3 achieved
the resolution of rac-3a with a comparable s value, but the con-
version slightly decreased.
Next, other aryl cycloalkyl carbinols were subjected to the ki-
netic resolution catalyzed by 2 to investigate the substrate scope.
The reactions were conducted using 0.6 equiv of benzoyl chloride
and 10 mol% catalyst 2 in CHCl3 to recover the unreacted alcohols
with a high optical purity (Scheme 1). Under these conditions, the
reaction of rac-3a proceeded with resolving efficiency (s ¼ 22),
similar to the reaction shown in Table 1, and (S)-alcohol was
recovered with 99% ee. The carbinol bonded to a cycloheptane
ring (rac-3b) was also resolved with s > 20, indicating that the
resolution is practically possible.1a The cyclopentyl and cyclo-
propyl carbinols (rac-3c-d) were also examined. Although cyclo-
pentyl carbinol was resolved with a moderate selectivity (s ¼ 15),
Table 1
Kinetic resolution of cyclohexyl(phenyl)methanol rac-3a by benzoylation using aminophosphinite catalyst 2.
Entry
Solvent
x
Yield (%)a (% ee)b of 3a
Yield (%)a (% ee)b of 4a
Conv. (%)c
sd
1
2
3
4
5
6
CHCl3
10
10
10
10
10
5
41 (80)
45 (66)
48 (65)
68 (39)
88 (4)
40 (82)
38 (71)
48 (84)
30 (88)
10 (80)
40 (86)
49
48
44
31
5
25
12
22
23
9
CH3CN
CH2Cl2
Cl(CH2)2Cl
Toluene
CHCl3
55 (63)
42
25
a
Isolated yields.
Determined by chiral HPLC analysis.
b
c
Conversion (%) ¼ 100 ꢀ ee of unreacted alcohol/(ee of unreacted alcohol þ ee of benzoate), see Ref. 15.
d
Selectivity factor ¼ k (fast-reacting enantiomer)/k (slow-reacting enantiomer), see Ref. 15.

298
N. Hara et al. / Tetrahedron 74 (2018) 296e302
Scheme 1. Kinetic resolution of aryl cycloalkyl carbinols.
The steric effect of substituents located close to a hydroxyl group
an excellent selectivity (s ¼ 106). The absolute configuration of the
main alcohols recovered from the reaction of these sterically hin-
dered carbinols was assumed to be R, similar to the reactions of 1-
arylethanols rac-5aef, because the optical rotation data showed
that the R isomers were enriched in the recovered alcohols ob-
tained from the reaction of rac-5g and rac-5i. On the other hand,
in secondary alcohols was also investigated. Similar reaction of a 1-
arylethanol bearing a methyl group at the ortho position on the
benzene ring (rac-5g) afforded the corresponding benzoate and
unreacted alcohol with a significantly increased selectivity factor
(s ¼ 13). Moreover, the selectivity factors increased with an increase
in the number of methyl groups on the benzene ring, and 2,6-
dimethylphenyl- and 2,4,6-trimethylphenyl carbinols (rac-5h, 5i)
could be resolved with s ¼ 20 and 33, respectively. Similar reaction
of a more sterically demanding substrate (rac-5j) proceeded with
carbinol with
a branched alkyl group, but not a sterically
demanding aryl group was also an effective substrate for the acy-
lative kinetic resolution catalyzed by 2. The reaction of 2-methyl-1-
phenylpropan-1-ol rac-5k was achieved with an acceptable
Scheme 2. Kinetic resolution of aryl acyclic alkyl carbinols.

N. Hara et al. / Tetrahedron 74 (2018) 296e302
299
stereoselectivity (s ¼ 25). In contrast to the result, a similar sub-
strate in which the alkyl group was not branched (rac-5l) was not
resolved with stereoselectivity. Interestingly, S isomer was the
preferentially recovered alcohol from the reaction of rac-5k
opposite to the reaction of other aryl acyclic alkyl carbinols. These
results obtained from the reactions of rac-5k indicate that
branching at the carbon atom adjacent to the carbinol carbon atom
significantly affected the recognition of substrates using catalyst 2.
Given that absolute configuration of recovered alcohols was in-
verse, a reactive intermediate seemed to recognize a substituent
around the carbinol carbon as the largest one in the following or-
der; a branched sp3 carbon (except for cyclopropyl) > a branched
sp2 carbon > a methyl group. The reactive intermediate could not
be unambiguously identified yet, but it is possible that the benzoyl
group was transferred to the hydroxyl group from the benzoyl
phosphonium salt generated from the catalyst 2 and benzoyl
chloride. The benzoyl phosphonium salt was a very bulky group.
Therefore, the present kinetic resolution seemed to be strictly
influenced by the steric interaction between the largest substituent
in the carbinol and benzoyl phosphonium moiety in the
intermediate.
chloride (253 mg, 1.8 mmol) was added dropwise to the mixture at
ꢁC. After the resulting mixture was stirred at 0 ꢁC for 5 h, the
0
molecular sieves were filtered with suction filtration. To the filtrate,
water was added, and the mixture was extracted with CHCl3. The
combined organic layers were washed with brine, dried over
Na2SO4, and concentrated under reduced pressure. The crude re-
action mixture was purified by flash column chromatography using
a mixture of ethyl acetate/n-hexane, affording the corresponding
benzoate and recovering the alcohol.
4.2.1. Cyclohexyl(phenyl)methanol (rac-3a)
Recovered alcohol (3a)16: 214 mg (37% yield), colorless solid;
28
25
[a
]
ꢂ30.9 (c 1.05, CH2Cl2) [lit. [
a
]
D
þ28.0 (c 1.0, CH2Cl2), 92% ee
D
(R)]; 1H NMR (CDCl3, 400 MHz)
d 7.36e7.24 (m, 5H), 4.37 (dd,
J ¼ 3.3, 7.2 Hz, 1H), 2.02e1.95 (m, 1H), 1.80e1.73 (m, 2H), 1.70e1.57
(m, 3H), 1.41e1.35 (m, 1H), 1.28e0.88 (m, 5H); HPLC (AD-H, hexane/
i-PrOH ¼ 99/1, flow rate ¼ 1.0 mL/min), retention times: 24.4 min
(major), 28.5 min (minor) (99% ee). Benzoate (4a): 501 mg (57%
yield), colorless solid; [
400 MHz)
a
]
29 ꢂ23.9 (c 1.00, CH2Cl2); 1H NMR (CDCl3,
D
d
8.10e8.07 (m, 2H), 7.58e7.53 (m, 1H), 7.47e7.42 (m,
2H), 7.38e7.30 (m, 4H), 7.28e7.24 (m, 1H), 5.74 (d, J ¼ 7.4 Hz, 1H),
1.98e1.87 (m, 2H), 1.79e1.61 (m, 3H), 1.54e1.47 (m, 1H), 1.30e0.98
(m, 5H); HRMS (ESI-TOF) m/z [M þ Na]þ, calcd for C20H22NaO2
317.1512, found 317.1516; HPLC (AD-H, hexane/i-PrOH ¼ 98/2, flow
rate ¼ 1.0 mL/min), retention times: 8.5 min (major), 11.1 min
(minor) (63% ee).
3. Conclusions
In this work, kinetic resolution of diverse secondary alcohols
was attempted by benzoylation reaction catalyzed by amino-
phosphinite organocatalyst 2. Although phenyl- or para-
substituted phenyl alkanols were not effective substrates, bulky
aryl cycloalkyl carbinols could be resolved with a practical level of
selectivity. The steric effect of the substituents located around
carbinols significantly affected the efficiency of the resolution, and
(2,4,6-trimethylphenyl)propan-1-ol was resolved with s ¼ 106.
Especially, branching of the alkyl group at the position adjacent to
the carbinol carbon atom of aryl alkyl carbinols significantly affect
the stereoselectivity and absolute configuration of the products.
4.2.2. Cycloheptyl(phenyl)methanol (rac-3b)
Recovered alcohol (3b)17: 279 mg (46% yield), colorless oil;
30
[a
]
ꢂ13.8 (c 1.20, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 7.36e7.24
D
(m, 5H), 4.47 (dd, J ¼ 3.3, 6.4 Hz, 1H), 1.92e1.81 (m, 2H), 1.78 (d,
J ¼ 3.3 Hz, 1H), 1.72e1.30 (m, 10H), 1.22e1.12 (m, 1H); HPLC (AD-H,
hexane/i-PrOH ¼ 99/1, flow rate ¼ 0.6 mL/min), retention times:
36.1 min (major), 41.1 min (minor) (92% ee). Benzoate (4b): 473 mg
31
(51% yield), colorless solid; [
(CDCl3, 400 MHz)
a]
ꢂ27.0 (c 1.32, CHCl3); 1H NMR
D
d
8.10e8.07 (m, 2H), 7.57e7.52 (m, 1H), 7.46e7.42
4. Experimental section
(m, 2H), 7.39e7.37 (m, 2H), 7.34e7.29 (m, 2H), 7.27e7.22 (m, 1H),
5.84 (d, J ¼ 7.2 Hz, 1H), 2.18e2.10 (m, 1H), 1.94e1.86 (m, 1H),
1.72e1.34 (m, 10H), 1.31e1.21 (m, 1H); HRMS (ESI-TOF) m/z
[M þ Na]þ, calcd for C21H24NaO2 331.1669, found 331.1665; HPLC
(AD-H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 1.0 mL/min), retention
times: 10.3 min (major), 12.9 min (minor) (78% ee).
4.1. General procedures
1H NMR spectra were performed using a Bruker Avance 400
spectrometer. Proton chemical shifts are reported in parts per
million (d, ppm) relative to the internal standard tetramethylsilane
(TMS,
d
0.0 ppm). High-resolution mass spectra were obtained
4.2.3. Cyclopentyl(phenyl)methanol (rac-3c)
using a Bruker micrOTOF II LC-MS spectrometer equipped with an
electrospray ionization source (ESI). All the high-resolution mass
spectra were performed using anhydrous CH3CN as the solvent.
Enantiomeric excess was determined by HPLC analysis using a Jasco
Gulliver series HPLC equipped with a Daicel Chiralcel column as
indicated below. All the peaks of HPLC were detected with 254-nm
UV light. Specific rotation was measured using a Jasco DIP-370
digital polarimeter. Flash column chromatography was performed
Recovered alcohol (3c)18: 286 mg (54% yield), colorless oil;
25
20
D
d
[a
]
ꢂ34.2 (c 1.06, CHCl3) [lit. [
a
]
ꢂ44.4 (c 0.9, CHCl3), >99% ee
D
(S)]; 1H NMR (CDCl3, 400 MHz)
7.35e7.24 (m, 5H), 4.40 (dd,
J ¼ 3.2, 8.4 Hz, 1H), 2.27e2.17 (m, 1H), 1.92e1.85 (m, 2H), 1.72e1.43
(m, 5H), 1.41e1.34 (m, 1H), 1.20e1.11 (m, 1H); HPLC (OB-H, hexane/
i-PrOH ¼ 95/5, flow rate ¼ 0.2 mL/min), retention times: 33.3 min
(major), 37.3 min (minor) (63% ee). Benzoate (4c): 372 mg (44%
26
yield), colorless oil; [
a]
ꢂ16.4 (c 1.06, CHCl3); 1H NMR (CDCl3,
D
using Cica-Merck Silica Gel 60 N (40e50
mm). All the reactions were
400 MHz) d 8.09e8.06 (m, 2H), 7.57e7.53 (m, 1H), 7.46e7.41 (m,
performed using dried glassware under nitrogen atmosphere. All
the solvents were purified by conventional methods before use.
Catalyst 2 was prepared as previously described.13b
4H), 7.34e7.31 (m, 2H), 7.28e7.24 (m, 1H), 5.79 (d, J ¼ 8.7 Hz, 1H),
2.57e2.47 (m, 1H), 1.90e1.84 (m, 1H), 1.72e1.46 (m, 6H), 1.32e1.22
(m, 1H); HRMS (ESI-TOF) m/z [M þ Na]þ, calcd for C19H20NaO2
303.1356, found 303.1351; HPLC (AD-H, hexane/i-PrOH ¼ 90/10,
flow rate ¼ 1.0 mL/min), retention times: 5.6 min (major), 6.8 min
(minor) (77% ee).
4.2. General procedure for the kinetic resolution of secondary
alcohols by catalytic benzoylation
A two-neck round-bottom flask containing powdered 4 Å mo-
lecular sieves (0.6 g) was dried under nitrogen atmosphere. A so-
lution of secondary alcohol (3 mmol) in CHCl3 (6 mL) was added to
the flask. Subsequently, catalyst 2 (108 mg, 0.3 mmol) and i-Pr2NEt
(233 mg, 1.8 mmol) were added to the solution, and benzoyl
4.2.4. Cyclopropyl(phenyl)methanol (rac-3d)
Recovered alcohol (3d)19: 188 mg (42% yield), colorless oil;
[a
]
26 ꢂ10.1 (c 1.01, CH2Cl2) [lit. [
a
d
]
28 ꢂ12.89 (c 0.57, CH2Cl2), 43% ee
D
D
(R)]; 1H NMR (CDCl3, 400 MHz)
7.44e7.41 (m, 2H), 7.38e7.33 (m,
2H), 7.31e7.26 (m, 1H), 4.02 (d, J ¼ 8.3 Hz, 1H), 1.94 (s, 1H), 1.27e1.18

300
N. Hara et al. / Tetrahedron 74 (2018) 296e302
(m, 1H), 0.68e0.61 (m, 1H), 0.59e0.53 (m, 1H), 0.51e0.45 (m, 1H),
0.41e0.35 (m, 1H); HPLC (OJ-H, hexane/i-PrOH ¼ 90/10, flow
rate ¼ 1.0 mL/min), retention times: 10.6 min (major), 9.5 min
4.2.8. Cyclohexyl(thiophen-2-yl)methanol (rac-3h)
Recovered alcohol (3h)24: 209 mg (35% yield), colorless oil;
[a
]
28 ꢂ13.8 (c 1.22, CHCl3) [lit. [
a
]
23 ꢂ2.3 (c 1.2, CHCl3), 20% ee (S)];
D
D
(minor) (35% ee). Benzoate (4d)20: 385 mg (51% yield), colorless oil;
1H NMR (CDCl3, 400 MHz)
d
7.26e7.23 (m, 1H), 6.98e6.93 (m, 2H),
26
[
a]
þ15.5 (c 1.13, CHCl3); 1H NMR (CDCl3, 400 MHz)
d
8.12e8.09
4.63 (d, J ¼ 7.2 Hz, 1H), 2.06e1.97 (m, 2H), 1.81e1.75 (m, 1H),
1.73e1.61 (m, 3H), 1.51e1.46 (m, 1H), 1.31e0.92 (m, 5H); HPLC (OB-
H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 0.7 mL/min), retention times:
17.7 min (major), 24.6 min (minor) (99% ee). Benzoate (4h): 535 mg
D
(m, 2H), 7.58e7.54 (m, 1H), 7.48e7.43 (m, 4H), 7.38e7.34 (m, 2H),
7.32e7.28 (m, 1H), 5.51 (d, J ¼ 8.5 Hz, 1H), 1.48e1.40 (m, 1H),
0.69e0.59 (m, 3H), 0.50e0.46 (m, 1H); HPLC (AD-H, hexane/i-
PrOH ¼ 90/10, flow rate ¼ 1.0 mL/min), retention times: 6.9 min
(major), 5.8 min (minor) (32% ee).
(59% yield), colorless oil; [
400 MHz)
a
]
29 þ5.5 (c 1.20, CHCl3); 1H NMR (CDCl3,
D
d
8.08e8.06 (m, 2H), 7.57e7.53 (m, 1H), 7.46e7.42 (m,
2H), 7.26e7.24 (m, 1H), 7.08e7.06 (m, 1H), 6.97e6.95 (m, 1H), 6.06
(d, J ¼ 8.0 Hz, 1H), 2.02e1.93 (m, 2H), 1.80e1.55 (m, 4H), 1.32e0.99
(m, 5H); HRMS (ESI-TOF) m/z [M þ Na]þ, calcd for C18H20NaO2S
323.1076, found 323.1076; HPLC (AD-H, hexane/i-PrOH ¼ 99/1, flow
rate ¼ 0.4 mL/min), retention times: 24.8 min (major), 30.5 min
(minor) (57% ee).
4.2.5. Cyclohexyl(pyridin-2-yl)methanol (rac-3e)
Recovered alcohol (3e)21: 154 mg (40% yield, reaction using
24
2 mmol of rac-3e), colorless solid; [
a
]
D
ꢂ19.7 (c 0.99, CHCl3) [lit.
20
[
a]
ꢂ3.7 (c 0.42, CHCl3), 63% ee]; 1H NMR (CDCl3, 400 MHz)
D
d
8.55e8.53 (m, 1H), 7.68e7.64 (m, 1H), 7.23e7.17 (m, 2H), 4.52 (d,
J ¼ 4.6 Hz, 1H), 4.09 (brs, 1H), 1.78e1.58 (m, 5H), 1.50e1.43 (m, 1H),
1.29e1.06 (m, 5H); HPLC (AD-H, hexane/i-PrOH ¼ 99/1, flow
rate ¼ 1.0 mL/min), retention times: 24.4 min (major), 27.9 min
(minor) (99% ee). Benzoate (4e): 327 mg (55% yield), colorless oil;
4.2.9. 1-Phenylethanol (rac-5a)
Recovered alcohol (5a)25: 93.2 mg (25% yield), colorless oil;
24
20
[a
]
þ18.1 (c 1.07, CH2Cl2) [lit. [
a
]
þ48.3 (c 1.0, CH2Cl2), 97% ee
D
D
(R)]; 1H NMR (CDCl3, 400 MHz)
d 7.39e7.33 (m, 4H), 7.30e7.25 (m,
[
a]
24 ꢂ32.1 (c 0.91, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.62e8.60
D
1H), 4.90 (q, J ¼ 6.4 Hz, 1H), 1.80 (brs, 1H), 1.53 (d, J ¼ 6.4 Hz, 3H);
HPLC (OJ-H, hexane/i-PrOH ¼ 95/5, flow rate ¼ 1.0 mL/min),
retention times: 11.2 min (minor), 13.0 min (major) (40% ee). Ben-
(m, 1H), 8.14e8.11 (m, 2H), 7.66e7.62 (m, 1H), 7.60e7.55 (m, 1H),
7.48e7.44 (m, 2H), 7.33 (d, J ¼ 7.8 Hz,1H), 7.20e7.16 (m, 1H), 5.85 (d,
J ¼ 6.4 Hz, 1H), 2.23e2.14 (m, 1H), 1.86e1.63 (m, 4H), 1.59e1.52 (m,
1H), 1.32e1.11 (m, 5H); HRMS (ESI-TOF) m/z [M þ Na]þ, calcd for
zoate (6a)26: 394 mg (58% yield), colorless oil; [
a]
24þ8.85 (c 1.03,
23
EtOH) [lit. [
400 MHz)
a]
ꢂ23 (c 1.2, EtOH), 92% ee (R)]; 1DH NMR (CDCl3,
D
C
19H21NNaO2 318.1465, found 318.1473; HPLC (AD-H, hexane/i-
d
8.08 (brd, J ¼ 7.4 Hz, 2H), 7.58e7.53 (m, 1H), 7.46e7.42
PrOH ¼ 99/1, flow rate ¼ 1.0 mL/min), retention times: 31.9 min
(m, 4H), 7.39e7.35 (m, 2H), 7.32e7.27 (m, 1H), 6.14 (q, J ¼ 6.6 Hz,
1H), 1.67 (d, J ¼ 6.6 Hz, 3H); HPLC (AD-H, hexane/i-PrOH ¼ 98/2,
flow rate ¼ 1.0 mL/min), retention times: 7.2 min (minor), 9.4 min
(major) (26% ee).
(major), 61.0 min (minor) (79% ee).
4.2.6. Cyclohexyl(pyridin-3-yl)methanol (rac-3f)
Recovered alcohol (3f)22: 106 mg (28% yield, reaction using
2 mmol of rac-3f), colorless solid; 1H NMR (CDCl3, 400 MHz)
4.2.10. 1-(4-Methoxyphenyl)ethanol (rac-5b)
Recovered alcohol (5b)27: 177 mg (39% yield), colorless oil;
d
8.45e8.44 (m, 2H), 7.67e7.64 (m, 1H), 7.27e7.24 (m, 1H), 4.42 (d,
30
20
[
a
]
þ12.1 (c 1.05, CHCl3) [lit. [
a
]
þ47.8 (c 1.60, CHCl3), 97% ee
D
D
J ¼ 6.9 Hz, 1H), 2.81 (brs, 1H), 1.96e1.93 (m, 1H), 1.79e1.75 (m, 1H),
1.71e1.57 (m, 3H), 1.42e1.38 (m, 1H), 1.28e0.90 (m, 5H); HPLC (AD-
H, hexane/i-PrOH ¼ 90/10, flow rate ¼ 1.0 mL/min), retention
times: 14.0 min (major), 10.0 min (minor) (2% ee). Benzoate (4f):
(R)]; 1H NMR (CDCl3, 400 MHz)
2H), 4.86 (q, J ¼ 6.4 Hz, 1H), 3.80 (s, 3H), 1.88 (brs, 1H), 1.48 (d,
6.4 Hz, 3H); HPLC (OJ-H, hexane/i-PrOH 98/2, flow
d 7.32e7.28 (m, 2H), 6.90e6.86 (m,
J
¼
¼
216 mg (37% yield), colorless solid; 1H NMR (CDCl3, 400 MHz)
d 8.65
rate ¼ 1.0 mL/min), retention times: 54.2 min (minor), 57.4 min
(major) (30% ee). Benzoate (6b)28: 360 mg (47% yield), colorless oil;
(d, J ¼ 2.0 Hz, 1H), 8.54e8.52 (m, 1H), 8.08e8.06 (m, 2H), 7.69e7.66
(m, 1H), 7.60e7.55 (m, 1H), 7.48e7.44 (m, 2H), 7.28e7.25 (m, 1H),
5.77 (d, J ¼ 7.4 Hz, 1H), 1.98e1.90 (m, 2H), 1.80e1.66 (m, 3H),
1.53e1.50 (m, 1H), 1.31e0.99 (m, 5H); HRMS (ESI-TOF) m/z
[M þ Na]þ, calcd for C19H21NNaO2 318.1465, found 318.1437; HPLC
(AD-H, hexane/i-PrOH ¼ 90/10, flow rate ¼ 1.0 mL/min), retention
times: 10.7 min (major), 17.0 min (minor) (5% ee).
24
[a
]
þ2.2 (c 1.22, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.07e8.05
D
(m, 2H), 7.56e7.52 (m, 1H), 7.44e7.37 (m, 4H), 6.91e6.88 (m, 2H),
6.10 (q, J ¼ 6.6 Hz,1H), 3.80 (s, 3H),1.66 (d, J ¼ 6.6 Hz, 3H); HPLC (OJ-
H, hexane/i-PrOH ¼ 95/5, flow rate ¼ 0.8 mL/min), retention times:
9.4 min (minor), 10.5 min (major) (23% ee).
4.2.11. 1-(4-Methylphenyl)ethanol (rac-5c)
Recovered alcohol (5c)29: 256 mg (63% yield), colorless oil;
27
20
4.2.7. Cyclohexyl(furan-2-yl)methanol (rac-3g)
[a
]
þ12.6 (c 0.99, CH2Cl2) [lit. [
a
d
]
D
þ18.5 (c 4.0, CH2Cl2), 90% ee
D
Recovered alcohol (3g)23: 189 mg (35% yield), yellow oil;
(R)]; 1H NMR (CDCl3, 400 MHz)
7.26 (d, J ¼ 8.1 Hz, 2H), 7.16 (d,
[
a]
24 ꢂ21.1 (c 1.03, CHCl3) [lit. [
a
]
20 ꢂ16.4 (c 1.1, CHCl3), 84% ee (S)];
J ¼ 8.1 Hz, 2H), 4.86 (q, J ¼ 6.4 Hz,1H), 2.34 (s, 3H),1.79 (brs,1H),1.48
(d, J ¼ 6.4 Hz, 3H); HPLC (OB-H, hexane/i-PrOH ¼ 95/5, flow
rate ¼ 1.0 mL/min), retention times: 7.9 min (minor), 8.7 min
D
D
1H NMR (CDCl3, 400 MHz)
d 7.37e7.36 (m, 1H), 6.33e6.32 (m, 1H),
6.21 (d, J ¼ 3.2 Hz, 1H), 4.38 (d, J ¼ 7.0 Hz, 1H), 2.01e1.94 (m, 1H),
1.83e1.74 (m, 3H), 1.72e1.63 (m, 2H), 1.47e1.41 (m, 1H), 1.32e0.92
(m, 5H); HPLC of benzoate derivative of 3g which was obtained by
kinetic resolution. (OJ-H, hexane/i-PrOH ¼ 99/1, flow rate ¼ 0.4 mL/
(major) (36% ee). Benzoate (6c)30: 266 mg (37% yield), colorless oil;
25
[a
]
þ5.2 (c 0.92, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.09e8.06
D
(m, 2H), 7.56e7.52 (m, 1H), 7.45e7.41 (m, 2H), 7.34 (d, J ¼ 8.0 Hz,
2H), 7.17 (d, J ¼ 8.0 Hz, 2H), 6.10 (q, J ¼ 6.6 Hz, 1H), 2.34 (s, 3H), 1.66
(d, J ¼ 6.6 Hz, 3H); HPLC (AD-H, hexane/i-PrOH ¼ 99/1, flow
rate ¼ 1.0 mL/min), retention times: 7.1 min (minor), 11.5 min
(major) (32% ee).
min), retention times: 17.6 min (major), 20.7 min (minor) (99% ee).
24
Benzoate (4g): 498 mg (58% yield), yellow oil; [
a
]
D
þ43.7 (c 1.15,
CHCl3); 1H NMR (CDCl3, 400 MHz)
d
8.08e8.05 (m, 2H), 7.57e7.52
(m, 1H), 7.45e7.38 (m, 3H), 6.36e6.31 (m, 2H), 5.84 (d, J ¼ 8.5 Hz,
1H), 2.20e2.10 (m, 1H), 1.98e1.91 (m, 1H), 1.79e1.64 (m, 3H),
1.55e1.48 (m, 1H), 1.34e0.99 (m, 5H); HRMS (ESI-TOF) m/z
[M þ Na]þ, calcd for C18H20NaO3 307.1305, found 307.1307; HPLC
(OJ-H, hexane/i-PrOH ¼ 99/1, flow rate ¼ 0.4 mL/min), retention
times: 17.7 min (minor), 19.9 min (major) (63% ee).
4.2.12. 1-(4-Chlorophenyl)ethanol (rac-5d)
Recovered alcohol (5d)31: 155 mg (33% yield), pale yellow oil;
[
a
]
30 þ28.1 (c 0.97, Et2O) [lit. [
a
]
25 ꢂ36.0 (c 1.0, Et2O), 72% ee (S)]; 1H
D
D
NMR (CDCl3, 400 MHz)
d
7.31 (s, 4H), 4.88 (q, J ¼ 6.4 Hz, 1H), 1.82

N. Hara et al. / Tetrahedron 74 (2018) 296e302
301
(brs,1H),1.48 (d, J ¼ 6.4 Hz, 3H); HPLC (OJ-H, hexane/i-PrOH ¼ 97/3,
flow rate ¼ 1.0 mL/min), retention times: 15.5 min (minor),
16.5 min (major) (54% ee). Benzoate (6d)32: 401 mg (51% yield),
4.2.17. 1-(2,4,6-Trimethylphenyl)ethanol (rac-5i)
Recovered alcohol (5i)38: 194 mg (39% yield), colorless solid;
28
27
[
a
]
þ55.0 (c 0.95, CHCl3) [lit. [
a
]
ꢂ60.6 (c 6.06, CHCl3), 95% ee
D
D
colorless oil; [
a
]
D
25 þ12.0 (c 1.01, CHCl3); 1H NMR (CDCl3, 400 MHz)
(S)]; 1H NMR (CDCl3, 400 MHz)
d
6.82 (s, 2H), 5.36 (q, J ¼ 6.8 Hz,1H),
d
8.08e8.05 (m, 2H), 7.59e7.54 (m, 1H), 7.47e7.42 (m, 2H),
2.41 (s, 6H), 2.24 (s, 3H), 1.67 (s, 1H), 1.52 (d, J ¼ 6.8 Hz, 3H); HPLC
(AD-H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 1.0 mL/min), retention
7.40e7.32 (m, 4H), 6.09 (q, J ¼ 6.6 Hz, 1H), 1.65 (d, J ¼ 6.6 Hz, 3H);
HPLC (AD-H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 0.5 mL/min),
retention times: 10.5 min (minor), 15.7 min (major) (36% ee).
times: 7.5 min (major), 8.3 min (minor) (85% ee). Benzoate (6i):
24
324 mg (40% yield), colorless oil; [
NMR (CDCl3, 400 MHz)
a
]
þ80.9 (c 0.94, CHCl3); 1H
D
d
8.07e8.05 (m, 2H), 7.56e7.52 (m, 1H),
4.2.13. 1-(4-(Trifluoromethyl)phenyl)ethanol (rac-5e)
7.45e7.41 (m, 2H), 6.83 (s, 2H), 6.51 (q, J ¼ 6.9 Hz, 1H), 2.51 (s, 6H),
2.24 (s, 3H), 1.69 (d, J ¼ 6.9 Hz, 3H); HRMS (ESI-TOF) m/z [M þ Na]þ,
calcd for C18H20NaO2 291.1356, found 291.1378; HPLC (AD-H, hex-
ane/i-PrOH ¼ 99/1, flow rate ¼ 0.4 mL/min), retention times:
11.0 min (major), 12.7 min (minor) (85% ee).
Recovered alcohol (5e)33: 186 mg (33% yield), colorless oil;
28
[
a]
þ14.9 (c 1.07, CHCl3) [lit. [
a
]
d
þ24.14 (c 1.41, CHCl3), >99% ee
D
D
(R)]; 1H NMR (CDCl3, 400 MHz)
7.61 (d, J ¼ 8.2 Hz, 2H), 7.49 (d,
J ¼ 8.2 Hz, 2H), 5.00e4.94 (m, 1H), 1.87 (d, J ¼ 3.6 Hz, 1H), 1.51 (d,
J ¼ 6.5 Hz, 3H); HPLC of a benzoate derivative of 5e which was
recovered after kinetic resolution. (AD-H, hexane/i-PrOH ¼ 95/5,
flow rate ¼ 0.8 mL/min), retention times: 5.5 min (major), 6.9 min
4.2.18. 1-(2,4,6-Trimethylphenyl)-1-propanol (rac-5j)
Recovered alcohol (5j)39: 263 mg (49% yield), colorless solid;
(minor) (61% ee). Benzoate (6e)30: 397 mg (45% yield), colorless oil;
[
a
]
24 þ37.8 (c 1.0, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 6.81 (s, 2H),
D
24
[
a]
þ19.6 (c 1.08, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.10e8.07
5.05 (dd, J ¼ 6.1, 8.4 Hz, 1H), 2.40 (s, 6H), 2.24 (s, 3H), 2.04e1.93 (m,
1H), 1.83e1.63 (m, 2H), 0.98 (t, J ¼ 7.4 Hz, 3H); HPLC (AD-H, hexane/
i-PrOH ¼ 95/5, flow rate ¼ 0.8 mL/min), retention times: 7.4 min
(major), 8.3 min (minor) (85% ee). Benzoate (6j): 376 mg (44% yield),
colorless oil; [
d
D
(m, 2H), 7.64e7.54 (m, 5H), 7.48e7.44 (m, 2H), 6.16 (q, J ¼ 6.6 Hz,
1H), 1.68 (d, J ¼ 6.6 Hz, 3H); HPLC (AD-H, hexane/i-PrOH ¼ 95/5,
flow rate ¼ 0.8 mL/min), retention times: 5.2 min (minor), 6.2 min
(major) (46% ee).
a
]
D
23 þ101.4 (c 1.07, CHCl3); 1H NMR (CDCl3, 400 MHz)
8.08e8.05 (m, 2H), 7.56e7.52 (m, 1H), 7.45e7.41 (m, 2H), 6.82 (s,
4.2.14. 1-(Naphtalen-2-yl)ethanol (rac-5f)
2H), 6.29 (dd, J ¼ 6.4, 8.9 Hz, 1H), 2.50 (s, 6H), 2.30e2.18 (m, 4H),
2.01e1.90 (m, 1H), 1.01 (t, J ¼ 7.4 Hz, 3H); HRMS (ESI-TOF) m/z
[M þ Na]þ, calcd for C19H22NaO2 305.1512, found 305.1513; HPLC
(AD-H, hexane/i-PrOH ¼ 200/1, flow rate ¼ 0.8 mL/min), retention
times: 7.6 min (major), 12.4 min (minor) (95% ee).
Recovered alcohol (5f)34: 197 mg (38% yield), colorless solid;
26
25
[
a]
þ12.7 (c 1.27, MeOH) [lit. [
a
d
]
ꢂ40.8 (c 0.90, MeOH), 79% ee
D
D
(S)]; 1H NMR (CDCl3, 400 MHz)
7.85e7.81 (m, 4H), 7.52e7.44 (m,
3H), 5.07 (q, J ¼ 6.4 Hz,1H),1.91 (s,1H),1.58 (d, J ¼ 6.4 Hz, 3H); HPLC
(OJ-H, hexane/i-PrOH ¼ 95/5, flow rate ¼ 1.0 mL/min), retention
times: 20.4 min (minor), 27.1 min (major) (33% ee). Benzoate (6f)35
:
4.2.19. 2-Methyl-1-phenyl-1-propanol (rac-5k)
27 þ13.6 (c 1.02, MeOH); 1H
Recovered alcohol (5k)40: 172 mg (38% yield), colorless oil;
498 mg (60% yield), colorless solid; [
NMR (CDCl3, 400 MHz)
a
]
D
27
23
D
d
d
8.12e8.09 (m, 2H), 7.89e7.80 (m, 4H),
[a
]
ꢂ42.4 (c 1.13, CHCl3) [lit. [
a
]
þ12.3 (c 1.2, CHCl3), 38.3% ee
D
(R)]; 1H NMR (CDCl3, 400 MHz)
7.36e7.24 (m, 5H), 4.37 (dd,
7.59e7.53 (m, 2H), 7.50e7.42 (m, 4H), 6.30 (q, J ¼ 6.6 Hz, 1H), 1.76
(d, J ¼ 6.6 Hz, 3H); HPLC (AD-H, hexane/i-PrOH ¼ 98/2, flow
rate ¼ 1.0 mL/min), retention times: 11.8 min (minor), 16.6 min
(major) (21% ee).
J ¼ 3.2, 6.8 Hz, 1H), 2.02e1.90 (m,1H), 1.80 (d, J ¼ 3.2 Hz,1H), 1.00 (d,
J ¼ 6.7 Hz, 3H), 0.80 (d, J ¼ 6.8 Hz, 3H); HPLC (OD-H, hexane/i-
PrOH ¼ 90/10, flow rate ¼ 0.5 mL/min), retention times: 11.4 min
(major), 12.6 min (minor) (97% ee). Benzoate (6k)41: 424 mg (56%
28
yield), colorless oil; [
400 MHz)
a]
ꢂ32.9 (c 1.36, CHCl3); 1H NMR (CDCl3,
4.2.15. 1-(2-Methylphenyl)ethanol (rac-5g)
D
Recovered alcohol (5g)36: 122 mg (30% yield), colorless oil;
d
8.11e8.08 (m, 2H), 7.58e7.54 (m, 1H), 7.47e7.43 (m,
[
a]
26 þ46.4 (c 1.00, EtOH) [lit. [
a
]
D þ61.9 (c 1.01, EtOH), 96% ee (R)];
2H), 7.39e7.31 (m, 4H), 7.29e7.24 (m, 1H), 5.73 (d, J ¼ 7.2 Hz, 1H),
2.31e2.19 (m, 1H), 1.05 (d, J ¼ 6.7 Hz, 3H), 0.90 (d, J ¼ 6.8 Hz, 3H);
HPLC (AD-H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 1.0 mL/min),
retention times: 7.9 min (major), 10.9 min (minor) (72% ee).
D
1H NMR (CDCl3, 400 MHz)
d 7.52e7.50 (m, 1H), 7.23e7.21 (m, 1H),
7.19e7.11 (m, 2H), 5.13 (q, J ¼ 6.4 Hz, 1H), 2.34 (s, 3H), 1.75 (s, 1H),
1.46 (d, J ¼ 6.4 Hz, 3H); HPLC (AD-H, hexane/i-PrOH ¼ 95/5, flow
rate ¼ 0.5 mL/min), retention times: 18.7 min (major), 21.0 min
(minor) (74% ee). Benzoate (6g)37: 268 mg (37% yield), colorless oil;
4.2.20. 1-Phenyl-1-propanol (rac-5l)
25 þ38.7 (c 0.99, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.10e8.07
Recovered alcohol (5l)25: 245 mg (60% yield), colorless oil; 1H
[
a
]
D
(m, 2H), 7.57e7.49 (m, 2H), 7.46e7.42 (m, 2H), 7.25e7.15 (m, 3H),
6.32 (q, J ¼ 6.6 Hz, 1H), 2.44 (s, 3H), 1.64 (d, J ¼ 6.6 Hz, 3H); HPLC
(OJ-H, hexane/i-PrOH ¼ 97/3, flow rate ¼ 0.5 mL/min), retention
times: 13.7 min (minor), 16.4 min (major) (71% ee).
NMR (CDCl3, 400 MHz) d 7.37e7.33 (m, 4H), 7.31e7.25 (m, 1H), 4.60
(t, J ¼ 6.6 Hz, 1H), 1.88e1.70 (m, 3H), 0.92 (t, J ¼ 7.4 Hz, 3H); HPLC
(OJ-H, hexane/i-PrOH ¼ 98/2, flow rate ¼ 1.0 mL/min), retention
times: 16.6 min, 17.7 min (2% ee). Benzoate (6l)32: 280 mg (39%
yield), colorless oil; 1H NMR (CDCl3, 400 MHz)
d 8.10e8.08 (m, 2H),
4.2.16. 1-(2,6-Dimethylphenyl)ethanol (rac-5h)
7.55e7.50 (m, 1H), 7.44e7.40 (m, 4H), 7.35e7.32 (m, 2H), 7.29e7.24
(m, 1H), 5.93 (t, J ¼ 6.8 Hz, 1H), 2.12e1.89 (m, 2H), 0.96 (t, J ¼ 7.4 Hz,
3H); HPLC (AD-H, hexane/i-PrOH ¼ 99/1, flow rate ¼ 1.0 mL/min),
retention times: 9.8 min, 15.2 min (3% ee).
Recovered alcohol (5h)3g: 157 mg (35% yield), colorless solid;
[
a
]
24 þ66.8 (c 0.98, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 7.05e6.98
D
(m, 3H), 5.39 (dq, J ¼ 2.2, 6.8 Hz, 1H), 2.45 (s, 6H), 1.71 (d, J ¼ 2.2 Hz,
1H), 1.54 (d, J ¼ 6.8 Hz, 3H); HPLC (OD-H, hexane/i-PrOH ¼ 95/5,
flow rate ¼ 1.0 mL/min), retention times: 7.7 min (minor), 9.4 min
(major) (95% ee). Benzoate (6h): 369 mg (48% yield), colorless oil;
Appendix A. Supplementary data
[
a]
24 þ98.0 (c 0.98, CHCl3); 1H NMR (CDCl3, 400 MHz)
d 8.07e8.05
D
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.tet.2017.11.062.
(m, 2H), 7.56e7.53 (m, 1H), 7.45e7.41 (m, 2H), 7.08e6.99 (m, 3H),
6.55 (q, J ¼ 7.0 Hz, 1H), 2.55 (s, 6H), 1.71 (d, J ¼ 7.0 Hz, 3H); HRMS
(ESI-TOF) m/z [M þ Na]þ, calcd for C17H18NaO2 277.1199, found
277.1200; HPLC (OD-H, hexane/i-PrOH ¼ 90/10, flow rate ¼ 0.3 mL/
min), retention times: 13.8 min (minor), 14.9 min (major) (69% ee).
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