Selective monobenzoylation of 1,2- and 1,3-diols catalyzed by Me 2SnCl2 in water (organic solvent free) under mild conditions

Article abstract of DOI:10.1021/jo202136a

We have developed an efficient method for selective monobenzoylation of 1,2- and 1,3-diols in water catalyzed by Me₂SnCl₂. Treatment of 1,2- and 1,3-diols with benzoyl chlorides, DMT-MM, and potassium carbonate in the presence of a catalytic amount of Me₂SnCl ₂ and DMAP in water at room temperature gave monobenzoates in up to 97% yield.

Full text of DOI:10.1021/jo202136a

Note
pubs.acs.org/joc
Selective Monobenzoylation of 1,2- and 1,3-Diols Catalyzed by
Me2SnCl2 in Water (Organic Solvent Free) under Mild Conditions
Wataru Muramatsu,* Julius M. William, and Osamu Onomura
Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, Nagasaki 852-8521, Japan
S
* Supporting Information
ABSTRACT: We have developed an efficient method for selective
monobenzoylation of 1,2- and 1,3-diols in water catalyzed by Me2SnCl2.
Treatment of 1,2- and 1,3-diols with benzoyl chlorides, DMT-MM, and
potassium carbonate in the presence of a catalytic amount of Me2SnCl2 and
DMAP in water at room temperature gave monobenzoates in up to 97%
yield.
Table 1. Selective Monobenzoylation of cis-Cyclooctane-1,2-
diol in Water
elective functionalization of polyols represents a major
current challenge in the efficient preparation of building
a
S
blocks that target the synthesis of natural products or new drug
candidates.1 In particular, regio- and stereoselective functiona-
lization of nonprotected polyols such as carbohydrates, inositols,
and natural products with nonenzymatic catalysts has been an
attractive challenge. Over the last several decades, catalytic
regioselective acylation of nonprotected monosaccharides2 and
natural products1a,d−f has been achieved in the presence of
organic and organometal catalysts. These catalytic reactions not
only facilitate protection of a particular hydroxy group in polyols,
but also realize natural product synthesis in a minimum number
of steps. However, the polyols that can be effectively targeted in
such reaction sequences are limited because most polyols are not
sufficiently soluble in organic solvents. Moreover, organic reac-
tions in water have recently attracted considerable attention
from the standpoint of green chemistry,3 and several acylation
methods including the Schotten−Baumann-type reaction have
been developed.4 However, their methods require special
conditions such as pH control,4b and nonenzymatic methods
for the selective acylation of polyols in water (organic solvent
free) has not been reported so far. This is because the most
fundamental problems are the hydrolysis of the acyl halides and
the corresponding ester products and unavoidable over-
acylation.1h To resolve such problems, we began an investigation
on catalytic selective monobenzoylation of 1,2- and 1,3-diols in
water under mild conditions as the first step for all polyols.
After a series of optimization studies, we found that the mono-
selective benzoylation of cis-cyclooctane-1,2-diol proceeded
efficiently in the presence of 10 mol % of Me2SnCl2, 10 mol %
of N,N-dimethylaminopyridine (DMAP), 1.0 equiv of potassium
catbonate, and 1.2 equiv of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-
methylmorpholinium chloride (DMT-MM)5 in water at room
temperature under air atmosphere (entry 1, Table 1; 97% yield
and no dibenzoate). Table 1 provides information about the effect
of a number of reaction parameters on the efficiency of mono-
selective benzoylation of cis-cyclooctane-1,2-diol. In the
absence of Me2SnCl2, essentially no reaction was observed
entry
variation from the “standard” conditions
yield of 1 (%)
1
none
97
<1
63
89
>99
15
69
42
41
95
72
70
63
2
no Me2SnCl2
3
no DMT-MM
4
no DMAP
5
under Ar, no DMAP
1 mol % of Me2SnCl2
Bu2SnCl2, instead of Me2SnCl2
Oc2SnCl2, instead of Me2SnCl2
Ph2SnCl2, instead of Me2SnCl2
Me2SnBr2, instead of Me2SnCl2
Me2SnO, instead of Me2SnCl2
Me2SnS, instead of Me2SnCl2
CuCl2, instead of Me2SnCl2
BzBr, instead of BzCl
Bz2O, instead of BzCl
BzOH, instead of BzCl
6
7
8
9
10
11
12
13
14
15
16
b
88
87
17
a
b
All data are the average of two experiments. Dibenzoate was
obtained in 2 and 6% yields.
(entry 2, Table 1). In the absence of DMT-MM, the yield was
dropped down to 63% (entry 3, Table 1). In addition, the use
of DMAP resulted in 89% yield with 5% yield of the known
intermediate 34 generated from DMT-MM and benzoic acid
(entry 4, Table 1). This reaction without a catalytic amount of
DMAP under Ar atmosphere underwent monobenzoylation in
Received: October 20, 2011
Published: November 7, 2011
© 2011 American Chemical Society
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The Journal of Organic Chemistry
Note
>99% yield (entry 5, Table 1). Use of a smaller amount of Me2-
SnCl2 gave monobenzoate 1 in unsatisfying yield (15% yield; entry 6,
Table 1). Me2SnBr2 can be employed in place of Me2SnCl2 as a cata-
lyst at the expense of a slight erosion in selectivity (entry 10, Table 1),
whereas the other Sn catalysts and Cu catalysts did not show
impressive activities (entries 7−9 and 11−13, Table 1). Treatment of
BzBr in place of BzCl afforded 1 in 79% yield with 6% of the
dibenzoate (entry 14, Table 1). Bz2O reacted with cis-cyclooctane-
1,2-diol to give 1 in good yield (entry 15, Table 1; 87% yield). BzOH,
which is normally generated from BzCl in water, was less reactive
under these reaction conditions (entry 16, Table 1; 17% yield).
Further, we examined the scope of this catalytic mono-
selective benzoylation with respect to electron-donating and
electron-withdrawing substituents on the electrophile (Table 2).
of benzoyl chloride shown in entries 13−15 (Table 2) yielded the
corresponding products in 44−64% yields.
With these achievements in hand, this catalytic system was used
in selective monobenzoylation with a wide range of commercially
available 1,2- and 1,3-diols (Table 3). All meso-1,2-diols containing
Table 3. Selective Monobenzoylation of 1,2- and 1,3-diols in
a
Water
Table 2. Selective Monobenzoylation of cis-Cyclooctane-1,2-
a
diol in Water
entry
R
product
yield (%)
1
2
3
4
5
6
7
8
9
2-Me-Ph
3-Me-Ph
4-Me-Ph
2-MeO-Ph
3-MeO-Ph
4-MeO-Ph
2-Cl-Ph
2
3
65
93
90
15
95
80
70
92
93
57
83
84
64
44
44
4
5
6
7
8
3-Cl-Ph
9
4-Cl-Ph
10
11
12
13
14
15
b
10
1-Nap
11
12
13
14
15
2-Nap
2-Thienyl
PhCH2
PhCH2CH2
PhCH2CH2CH2
16
a
b
All data are the average of two experiments. Dibenzoate was obtained
in 12% yield.
In the case of the benzoyl chlorides with electron-danating
groups at meta and para positions, the benzoylation proceeded
in 80−95% yields with no formation of dibenzoates (entries 2, 3,
5 and 6, Table 2). Similarly, use the benzoyl chlorides with
electron-withdrawing groups at meta and para positions afforded
the corresponding monobenzoates 9 and 10 in 92 and 93%
yield, respectively (entries 8 and 9, Table 2). On the other hand,
the benzoyl chlorides with these substituents at ortho position
gave relatively poor yields in this catalytic monobenzoylation
(entries 1, 4 and 7, Table 2; 65, 15, and 69% yield, respectively).
This trend can be attributed to the effect of steric hindrance at
the ortho position. We have also demonstrated the mono-
selective protection of cis-cyclooctane-1,2-diol using the other
acyl reagents in water. 2-Naphthoyl chloride afforded the
monoacylate 12 in 82% yield, whereas 1-naphthoyl chloride
afforded a lower yield of the monoprotected product 11 with
12% yield of the diacylate (entries 10 and 11, Table 2). Reaction
of 2-thiophenecarbonyl chloride with cis-cyclooctane-1,2-diol
yielded in 84% of the monothionyl product 13 (entry 12, Table 2).
Moreover, the catalytic selective monoprotection using homologues
a
b
All data are the average of two experiments. The ratio was calculated
1
by H NMR.
cyclic or acyclic diols were also monobenzoylated in good yields
(entries 1−6, 9, and 10, Table 3). However, the catalytic
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Note
monobenzoylation using trans-cyclic-1,2-diols did not give any
isolatable products because of the instability of coordination
intermediate resulting from Me2SnCl2 and trans-cyclic-1,2-diols. In
the case of cis-1,2-dihydroxyindan (entry 7, Table 3), the catalytic
reaction afforded the two regioisomers in a 1:2 ratio with 93%
overall yield. Using one of the less active diols, catechol, the
reaction with 1.2 equiv of BzCl served the corresponding
monobenzoate in 30% yield (entry 8, Table 3). Furthermore,
rac-acyclic diols (entries 11 and 12, Table 3) and 1,3-diols (entries
13 and 14, Table 3) were also converted to the corresponding
monobenzoates in moderate yields.
(i) route A, where an active intermediate generated by depro-
tonation of the stannylene complex 33 reacts directly with
benzoyl chloride; (ii) route B, where 33 reacts with an active
intermediate 34 generated by the condensation of BzOH with
DMT-MM; and (iii) route C, where 33 reacts with the acyl
pyridinium intermediate 35 generated from 34 with DMAP
(Scheme 3). Considering from the results of entries 3, 4, and 15
Scheme 3. Proposal Mechanism of Catalytic Monobenzoylation
in Water
Next, we demonstrated selective monobenzoylation of 1,2-
diols in the presence of primary and secondary hydroxy groups.
When rac-phenylethane-1,2-diol was treated under these cata-
lytic conditions, the primary hydroxy group of rac-phenylethane-
1,2-diol was selectively benzoylated in 92% yield (Scheme 1a).
Scheme 1. Selective and Competitive Monobenzoylation in
Water
in Table 1, about 65% of monobenzoate 1 is generated from
route A. Also, about 25 and 10% of 1 are obtained through
route B and C, respectively.
In conclusion, a catalytic process for the benzoylation of
1,2- and 1,3-diols in water (organic solvent free) with high
monoselectivity under mild conditions has been developed.
The catalytic reaction can be conveniently carried out and
widely applied in water because it does not require toxic and
flammable organic solvents. The method will provide not only a
new approach to an environmentally benign process for
esterification, but also useful selective protection techniques
of a hydroxy group in polyols in a minimum number of steps.
Furthermore, competitive benzoylation between cis-cyclooctane-
1,2-diol and rac-cyclooctane-methanol gave 1 selectively in 95%
yield with no detection of 32 (Scheme 1b).
In addition, we briefly investigated the asymmetric benzoyla-
tion of meso-1,2-diols. Using catalytic amount of several Sn cata-
lysts with (R,R)-PhBox,6 the catalytic reaction provided the
desired products with no enantiomeric excess. After Sn
catalyst was replaced to CuCl2, the enantiomeric excess was
improved to provide (1S,2R)-1 and (1S,2R)-25 with 60 and
99% ee, respectively (Scheme 2a and 2b).
EXPERIMENTAL SECTION
■
General Procedure for Selective Monobenzoylation of 1,2-
and 1,3-Diols in Water. K2CO3 (138 mg, 1.0 mmol), DMT-MM
(including 15.6% water, 393 mg, 1.2 mmol), 4-dimethylaminopyridine
(12.2 mg, 0.10 mmol), and benzoyl chloride (139 mL, 1.2 mmol)
were added to a suspension of a mixture of meso-1,2-cyclooctanediol
(144 mg, 1.0 mmol) and Me2SnCl2 (22.0 mg, 0.10 mmol) in purified
water (6.0 mL) at room temperature under air. After stirring for 24 h,
the reaction mixture was quenched with saturated aqueous NH4Cl and
extracted with ethyl acetate. The organic layer was washed with water
and brine, dried with MgSO4, filtrated, and concentrated in vacuo. The
residue was purified by SiO2 column chromatography (n-hexane/ethyl
acetate = 10/1) to give cis-2-hydroxycyclooctyl benzoate 1 (240.2 mg,
97%) as colorless oil.
Scheme 2. Asymmetric Benzoylation of meso-1,2-Diols in
Water
cis-2-Hydroxycyclooctyl Benzoate (1).7e,f Colorless oil: H NMR
1
(400 MHz, CDCl3) δ 8.06−8.03 (m, 2H), 7.59−7.42 (m, 3H), 5.32
(dt, J = 9.3, 2.4 Hz, 1H), 4.15−4.08 (m, 1H), 2.32 (br s, 1H), 2.31−
2.10 (m, 1H), 2.00−1.20 (m, 11H); 13C NMR (100 MHz, CDCl3) δ
166.2, 133.0, 130.3, 129.6 (2), 128.4 (2), 77.7, 71.9, 30.6, 27.9, 26.9,
25.6, 24.2, 22.0; IR (neat) 3460, 2920, 1709, 1271, 1109 cm−1; MS
m/z (rel intensity) 248 (M+, 15), 205 (60), 143 (40), 105 (100),
77 (45); HRMS calcd for C15H20O3 (M+) 248.1412, found 248.1400.
Finally, we proposed that the catalytic monobenzoylation
results from the domination of three competitive pathways:
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Note
1
cis-2-Hydroxycyclooctyl 2-Methylbenzoate (2). Colorless oil: H
NMR (400 MHz, CDCl3) δ 7.89 (dd, J = 8.2, 1.3 Hz, 1H), 7.39 (td,
J = 7.4, 1.3 Hz, 1H), 7.30−7.20 (m, 2H), 5.30 (dt, J = 8.9, 2.3 Hz, 1H),
4.08 (ddd, J = 8.9, 4.3, 2.6 Hz, 1H), 2.60 (s, 3H), 2.36 (br s, 1H),
2.30−2.10 (m, 1H), 2.00−1.50 (m, 11H); 13C NMR (100 MHz,
CDCl3) δ 167.2, 140.0, 131.9, 131.6, 130.4, 129.8, 125.7, 77.4, 71.8,
30.5, 27.9, 26.9, 25.6, 24.3, 22.0, 21.7; IR (neat) 3418, 2924, 1709,
1252, 1076 cm−1; MS m/z (rel intensity) 262 (M+, 35), 219 (20), 143
(40), 119 (100), 91 (80); HRMS calcd for C16H22O3 (M+) 262.1569,
found 262.1549.
(100 MHz, CDCl3) δ 165.4, 133.2, 132.6, 131.5, 131.0, 130.5, 126.7,
78.7, 71.6, 30.1, 27.5, 27.0, 25.3, 24.7, 21.8; IR (neat) 3422, 2922,
1713, 1290, 1115 cm−1; MS m/z (rel intensity) 282 (M+, 10), 239
(40), 157 (35), 139 (100), 126 (35); HRMS calcd for C15H19ClO3
(M+) 282.1023, found 282.1017.
cis-2-Hydroxycyclooctyl 4-Chlorobenzoate (10). White solid: mp
67−68 °C; 1H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 8.5, 2H), 7.42
(d, J = 8.5, 2H), 5.31 (dt, J = 9.3, 2.0 Hz, 1H), 4.10 (ddd, J = 9.3, 4.1,
2.4 Hz, 1H), 2.30−2.00 (m, 2H), 2.00−1.50 (m, 11H); 13C NMR
(100 MHz, CDCl3) δ 165.4, 139.5, 131.0 (2), 128.8, 128.8 (2), 78.1,
71.9, 30.7, 27.9, 26.9, 25.7, 24.1, 22.1; IR (neat) 3421, 2922, 1715,
1273, 1105 cm−1; MS m/z (rel intensity) 282 (M+, 10), 239 (30), 157
(25), 139 (100), 126 (35); HRMS calcd for C15H19ClO3 (M+)
282.1023, found 282.1017.
1
cis-2-Hydroxycyclooctyl 3-Methylbenzoate (3). Colorless oil: H
NMR (400 MHz, CDCl3) δ 7.85−7.83 (m, 2H), 7.39−7.30 (m, 2H),
5.31 (dt, J = 9.1, 2.2 Hz, 1H), 4.10 (ddd, J = 9.1, 4.3, 2.6 Hz, 1H), 2.40
(s, 3H), 2.30−2.10 (m, 1H), 2.25 (br s, 1H), 2.00−1.50 (m, 11H); 13C
NMR (100 MHz, CDCl3) δ 166.4, 138.2, 133.8, 130.3, 130.1, 128.3,
126.7, 77.6, 71.9, 30.5, 27.9, 26.9, 25.6, 24.2, 22.0, 21.2; IR (neat)
3458, 2920, 1707, 1277, 1107 cm−1; MS m/z (rel intensity) 262 (M+,
70), 219 (100), 143 (60), 119 (85), 91 (75); HRMS calcd for
C16H22O3 (M+) 262.1569, found 262.1560.
cis-2-Hydroxycyclooctyl 1-Naphthoate (11). Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.88 (d, J = 8.5 Hz, 1H), 8.14 (d, J =
7.3 Hz, 1H), 7.99 (d, J = 8.3 Hz, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.60 (t,
J = 7.7 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.8 Hz, 1H), 5.41
(dt, J = 9.4, 2.3 Hz, 1H), 4.20−4.10 (m, 1H), 2.42 (br s, 1H), 2.33−
2.17 (m, 1H), 2.00−1.50 (m, 11H); 13C NMR (100 MHz, CDCl3) δ
167.1, 133.8, 133.3, 131.2, 129.9, 128.5, 127.7, 127.4, 126.2, 125.6,
124.4, 77.7, 71.8, 30.5, 27.9, 26.9, 25.6, 24.4, 22.0; IR (neat) 3447,
2922, 1701, 1240, 1134 cm−1; MS m/z (rel intensity) 298 (M+, 25),
172 (35), 155 (100), 127 (35), 98 (25); HRMS calcd for C19H22O3
(M+) 298.1569, found 298.1568.
cis-2-Hydroxycyclooctyl 2-Naphthoate (12). White solid: mp 80−
81 °C; 1H NMR (400 MHz, CDCl3) δ 8.58 (s, 1H), 8.04 (dd, J = 8.7,
1.6 Hz, 1H), 7.92 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 8.5 Hz, 2H), 7.59−
7.49 (m, 1H), 5.37 (dt, J = 9.1, 2.3 Hz, 1H), 4.14 (ddd, J = 9.1, 3.8, 2.5
Hz, 1H), 2.52 (br s, 1H), 2.30−2.18 (m, 1H), 2.00−1.50 (m, 11H);
13C NMR (100 MHz, CDCl3) δ 166.3, 135.4, 132.4, 131.0, 129.2,
128.2, 128.1, 127.7, 127.5, 126.6, 125.1, 77.8, 71.8, 30.6, 27.9, 26.9,
25.6, 24.2, 22.0; IR (neat) 3534, 2920, 1697, 1229, 1132 cm−1; MS
m/z (rel intensity) 298 (M+, 50), 172 (70), 155 (100), 127 (90), 98
(50); HRMS calcd for C19H22O3 (M+) 298.1569, found 298.1561.
cis-2-Hydroxycyclooctyl 2-Thiophenecarboxylate (13). Colorless oil:
1H NMR (400 MHz, CDCl3) δ 7.82 (dd, J = 2.7, 1.2 Hz, 1H), 7.58−
7.55 (m, 1H), 7.13−7.09 (m, 1H), 5.28−5.25 (m, 1H), 4.09−4.06
(m, 1H), 2.31 (br s, 1H), 2.25−2.10 (m 1H), 2.00−2.50 (m, 11H);
13C NMR (100 MHz, CDCl3) δ 161.8, 133.9, 133.4, 132.4, 127.7,
78.0, 71.8, 30.4, 27.8, 26.8, 25.6, 24.1, 22.0; IR (neat) 3485, 2922,
1694, 1260, 1092 cm−1; MS m/z (rel intensity) 255 (M + H+, 50),
237 (20), 154 (15), 111 (100), 69 (50); HRMS calcd for C13H19O3S
(M + H+) 255.1049, found 255.1064.
1
cis-2-Hydroxycyclooctyl 4-Methylbenzoate (4). Colorless oil: H
NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 2H), 7.23 (d, J =
8.3 Hz, 2H), 5.29 (dt, J = 9.0, 2.2 Hz, 1H), 4.08 (ddd, J = 9.0, 4.1,
2.4 Hz, 1H), 2.48 (br s, 1H), 2.40 (s, 3H), 2.25−2.10 (m, 1H), 2.00−
1.50 (m, 11H); 13C NMR (100 MHz, CDCl3) δ 166.2, 143.7, 129.6
(2), 129.0 (2), 127.6, 77.5, 71.9, 30.5, 27.9, 26.8, 25.6, 24.2, 22.0, 21.6;
IR (neat) 3429, 2922, 1694, 1273, 1107 cm−1; MS m/z (rel intensity)
262 (M+, 15), 219 (45), 143 (20), 119 (100), 91 (45); HRMS calcd
for C16H22O3 (M+) 262.1569, found 262.1549.
cis-2-Hydroxycyclooctyl 2-Methoxybenzoate (5). Colorless oil:
1H NMR (400 MHz, CDCl3) δ 7.80 (dd, J = 7.7, 1.8 Hz, 1H), 7.48
(ddd, J = 8.7, 7.0, 1.4 Hz, 1H), 7.04−6.97 (m, 2H), 5.30 (dt, J = 9.8,
2.5 Hz, 1H), 4.10−4.00 (m, 1H), 3.90 (s, 3H), 2.94 (br s, 1H), 2.23−
2.10 (m, 1H), 2.00−1.50 (m, 11H); 13C NMR (100 MHz, CDCl3)
δ 166.1, 158.6, 133.5, 131.8, 120.6, 120.5, 111.9, 77.8, 71.6, 56.0, 29.7,
27.4, 26.7, 25.3, 25.0, 22.3; IR (neat) 3507, 2916, 1680, 1277, 1099
cm−1; MS m/z (rel intensity) 278 (M+, 5), 235 (10), 152 (5), 135
(100), 98 (15); HRMS calcd for C16H22O4 (M+) 278.1518, found
278.1520.
cis-2-Hydroxycyclooctyl 3-Methoxybenzoate (6). Colorless oil:
1H NMR (400 MHz, CDCl3) δ 7.63 (ddd, J = 7.9, 1.5, 1.0 Hz, 1H),
7.56 (dd, J = 2.7, 1.5 Hz, 1H), 7.35 (t, J = 7.9 Hz, 1H), 7.10 (ddd, J =
7.9, 2.7, 1.0 Hz, 1H), 5.31 (dt, J = 9.0, 2.3 Hz, 1H), 4.10 (ddd, J = 9.0,
4.2, 2.4 Hz, 1H), 3.85 (s, 3H), 2.34 (br s, 1H), 2.23−2.13 (m, 1H),
2.00−1.50 (m, 11H); 13C NMR (100 MHz, CDCl3) δ 166.1, 159.5,
131.7, 129.4, 121.9, 119.2, 114.3, 77.9, 71.9, 55.4, 30.6, 27.9, 26.8, 25.7,
24.1, 22.0; IR (neat) 3431, 2922, 1709, 1275, 1101 cm−1; MS m/z (rel
intensity) 278 (M+, 15), 235 (10), 152 (20), 135 (100), 98 (15);
HRMS calcd for C16H22O4 (M+) 278.1518, found 278.1503.
cis-2-Hydroxycyclooctyl 4-Methoxybenzoate (7). White solid: mp
cis-2-Hydroxycyclooctyl Phenylacetylate (14). Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 7.40−7.24 (m, 5H), 5.05 (dt, J = 9.3,
2.4 Hz, 1H), 3.93−3.88 (m, 1H), 3.65 (s, 2H), 2.10−1.40 (m, 13H);
13C NMR (100 MHz, CDCl3) δ 171.1, 134.0, 129.1 (2), 128.6 (2),
127.2, 77.5, 71.7, 41.7, 30.1, 27.6, 26.9, 25.3, 24.5, 21.7; IR (neat)
3474, 2922, 1724, 1256, 1159 cm−1; MS m/z (rel intensity) 263 (M +
H+, 25), 245 (10), 154 (100), 136 (70), 91 (55); HRMS calcd for
C16H23O3 (M + H+) 263.1642, found 263.1660.
1
86−87 °C; H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.9 Hz, 2H),
6.92 (d, J = 8.9 Hz, 1H), 5.30−5.26 (m, 1H), 4.15−4.05 (m, 1H), 3.86
(s, 3H), 2.33 (br s, 1H), 2.24−2.12 (m, 1H), 2.00−1.50 (m, 11H); 13C
NMR (100 MHz, CDCl3) δ 166.0, 163.4, 131.6 (2), 122.7, 113.6 (2),
77.4, 72.0, 55.4, 30.6, 28.1, 26.9, 25.7, 24.2, 22.1; IR (neat) 3505, 2916,
1680, 1279, 1099 cm−1; MS m/z (rel intensity) 278 (M+, 5), 235 (15),
152 (20), 135 (100), 98 (15); HRMS calcd for C16H22O4 (M+)
278.1518, found 278.1508.
cis-2-Hydroxycyclooctyl Phenylpropanoate (15). Colorless oil:
1H NMR (400 MHz, CDCl3) δ 7.40−7.15 (m, 5H), 5.03 (dt, J = 9.3,
2.4 Hz, 1H), 3.90−3.80 (m, 1H), 2.96 (t, J = 7.6 Hz, 2H), 2.67 (t, J =
7.6 Hz, 2H), 2.10−1.40 (m, 13H); 13C NMR (100 MHz, CDCl3)
δ 172.4, 140.3, 128.5 (2), 128.2 (2), 126.3, 77.0, 71.5, 36.0, 31.0, 30.1,
27.5, 26.9, 25.4, 24.4, 21.7; IR (neat) 3478, 2922, 1724, 1260, 1161
cm−1; MS m/z (rel intensity) 277 (M + H+, 10), 259 (10), 151 (30),
133 (40), 55 (100); HRMS calcd for C17H25O3 (M + H+) 277.1778,
found 277.1813.
cis-2-Hydroxycyclooctyl 2-Chlorobenzoate (8). White solid: mp
1
67−68 °C; H NMR (400 MHz, CDCl3) δ 7.97 (dd, J = 8.7, 1.9 Hz,
2H), 7.40 (dd, J = 8.7, 1.9 Hz, 2H), 5.30 (dt, J = 9.2, 2.0 Hz, 1H),
4.12−4.07 (m, 1H), 2.37 (br s, 1H), 2.30−2.10 (m, 1H), 2.00−1.50
(m, 11H); 13C NMR (100 MHz, CDCl3) δ 165.3, 139.5, 130.9 (2),
128.8, 128.7 (2), 78.0, 71.8, 30.7, 27.9, 26.8, 25.7, 24.1, 22.0; IR (neat)
3422, 2922, 1713, 1290, 1115 cm−1; MS m/z (rel intensity) 282 (M+,
10), 239 (45), 157 (30), 139 (100), 126 (40); HRMS calcd for
C15H19ClO3 (M+) 282.1023, found 282.1007.
1
cis-2-Hydroxycyclooctyl Phenylbutanoate (16). Colorless oil: H
NMR (400 MHz, CDCl3) δ 7.35−7.10 (m, 5H), 5.05 (dt, J = 9.3,
2.4 Hz, 1H), 4.00−3.88 (m, 1H), 2.66 (t, J = 7.6 Hz, 2H), 2.34 (t, J =
7.6 Hz, 2H), 2.17 (br s, 1H), 2.10−1.90 (m, 3H), 1.90−1.40 (m,
11H); 13C NMR (100 MHz, CDCl3) δ 173.0, 141.2, 128.4 (2), 128.3
(2), 126.0, 76.7, 71.6, 35.0, 33.8, 30.2, 27.7, 26.9, 26.5, 25.3, 24.4, 21.8;
IR (neat) 3487, 2922, 1724, 1246, 1144 cm−1; MS m/z (rel intensity)
1
cis-2-Hydroxycyclooctyl 3-Chlorobenzoate (9). Colorless oil: H
NMR (400 MHz, CDCl3) δ 7.83 (dd, J = 7.7, 1.6 Hz, 1H), 7.50−7.39
(m, 2H), 7.38−7.30 (m, 1H), 5.35−5.30 (m, 1H), 4.13−4.08 (m, 1H),
2.33 (br s, 1H), 2.30−2.15 (m, 1H), 2.00−1.50 (m, 11H); 13C NMR
757
dx.doi.org/10.1021/jo202136a | J. Org. Chem. 2012, 77, 754−759

The Journal of Organic Chemistry
Note
291 (M + H+, 10), 273 (10), 165 (25), 147 (100), 109 (40), 55 (40);
HRMS calcd for C18H27O3 (M + H+) 291.1955, found 291.1988.
cis-2-Hydroxycyclopentyl Benzoate (17).7c−f Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.07−8.00 (m, 2H), 7.60−7.50 (m, 1H),
7.50−7.40 (m, 2H), 5.30−5.20 (m, 1H), 4.40−4.25 (m, 1H), 2.20−
1.50 (m, 7H); 13C NMR (100 MHz, CDCl3) δ 166.4, 133.1, 130.1,
129.6 (2), 128.4 (2), 77.4, 73.4, 30.9, 28.2, 19.5; IR (neat) 3449, 2968,
1697, 1271, 1115 cm−1; MS m/z (rel intensity) 206 (M+, 5), 188 (25),
123 (70), 105 (100), 77 (95), 55 (75); HRMS calcd for C12H14O3
(M+) 206.0943, found 206.0941.
(m, 2H), 2.84 (br s, 1H); 13C NMR (100 MHz, CDCl3) δ 166.5,
141.7, 139.1, 133.1, 129.7, 129.6 (2), 128.7, 128.2 (2), 127.2, 125.1,
124.7, 76.3, 75.1, 35.6; IR (neat) 3358, 3063, 1717, 1271, 1099 cm−1;
MS m/z (rel intensity) 255 (M + H+, 5), 237 (50), 154 (30), 105
(95), 77 (35), 55 (60); HRMS calcd for C16H15O3 (M + H+)
255.1016, found 255.1008.
2-Benzoyloxyphenol (24).9 White solid: mp 132−133 °C (lit.9 mp
1
132−133 °C); H NMR (400 MHz, CDCl3) δ 8.23 (d, J = 7.3 Hz,
2H), 7.69−7.64 (m, 1H), 7.55−7.50 (m, 3H), 7.20−7.13 (m, 2H),
7.03−6.95 (m, 2H), 5.95 (br s, 1H); 13C NMR (100 MHz, CDCl3) δ
165.2, 147.3, 138.7, 134.0, 130.4 (2), 128.7, 128.7 (2), 127.1, 122.5,
121.0, 117.9; IR (neat) 3408, 2803, 1713, 1595, 710 cm−1; MS m/z
(rel intensity) 214 (M+, 10), 105 (100), 77 (50), 51 (10); HRMS
calcd for C13H10O3 (M+) 214.0630, found 214.0627.
cis-2-Hydroxycyclohexyl Benzoate (18).7a−f Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.20−8.00 (m, 2H), 7.70−7.30 (m,
3H), 5.30−5.10 (m, 1H), 4.66 (br s, 1H), 4.10−3.90 (m, 1H), 2.10−
1.93 (m, 1H), 1.93−1.55 (m, 5H), 1.55−1.30 (m, 2H); 13C NMR
(100 MHz, CDCl3) δ 166.2, 132.9, 130.3, 129.5 (2), 128.3 (2), 74.4,
69.5, 30.2 (2), 27.3, 21.6; IR (neat) 3420, 2938, 1695, 1271,
1109 cm−1; MS m/z (rel intensity) 221 (M+, 5), 135 (2), 105 (100),
77 (90), 70 (40); HRMS calcd for C13H16O3 (M+) 220.1099, found
220.1086.
anti-2-Benzoyloxy-1,2-diphenylethanol (25).7c,e,f White solid: mp
162−164 °C (lit.7c mp 161−163 °C); 1H NMR (400 MHz, CDCl3) δ
8.00 (d, J = 7.1 Hz, 2H), 7.53 (t, J = 7.3 Hz, 1H), 7.40 (dd, J = 7.3,
7.1 Hz, 2H), 7.31−7.10 (m, 10H), 6.15 (d, J = 5.9 Hz, 1H), 5.14 (dd,
J = 5.9, 3.6 Hz, 1H), 2.30 (d, J = 3.6 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 165.4, 139.5, 136.5, 133.1, 130.0, 129.6 (2), 128.4 (2), 128.4
(2), 128.3 (2), 128.1 (2), 127.6 (2), 127.0 (2), 79.5, 76.6; IR (neat)
3524, 3046, 1697, 1275, 1117 cm−1; MS m/z (rel intensity) 318 (M+,
5), 212 (55), 107 (45), 105 (100), 77 (40), 51 (5); HRMS calcd for
C21H18O3 (M+) 318.1256, found 318.1248.
1
cis-2-Hydroxycycloheptyl Benzoate (19). Colorless oil: H NMR
(400 MHz, CDCl3) δ 8.07−8.04 (m, 2H), 7.58−7.53 (m, 1H), 7.46−
7.27 (m, 2H), 5.25 (dt, J = 8.3, 2.4 Hz, 1H), 4.09−4.05 (m, 1H), 2.54
(br s, 1H), 2.15−2.00 (m, 1H), 1.90−1.24 (m, 9H); 13C NMR
(100 MHz, CDCl3) δ 166.3, 133.0, 130.3, 129.6 (2), 128.4 (2), 78.6,
72.8, 31.7, 28.0, 26.9, 22.8, 22.1; IR (neat) 3424, 2930, 1709, 1271,
1113 cm−1; MS m/z (rel intensity) 235 (M + H+, 80), 154 (20), 105
(100), 77 (30), 55 (20); HRMS calcd for C14H19O3 (M + H+)
235.1329, found 235.1348.
anti-2-Benzoyloxy-1,2-ditolunylethanol (26). White solid: mp
1
158−159 °C; H NMR (400 MHz, CDCl3) δ 8.10−8.07 (m, 2H),
7.58−7.51 (m, 1H), 7.45−7.41 (m, 2H), 7.13−7.00 (m, 8H), 6.06 (d,
J = 7.3 Hz, 1H), 5.02 (d, J = 7.3 Hz, 1H), 2.70 (br s, 1H), 2.27 (s, 3H),
2.26 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 165.8, 137.8, 137.6,
136.1, 133.9, 133.1, 130.1, 129.7 (2), 128.9 (2), 128.8 (2), 128.4 (2),
127.2 (2), 127.0 (2), 80.4, 76.9, 21.1 (2); IR (neat) 3493, 2922, 1717,
1273, 1111 cm−1; MS m/z (rel intensity) 318 (M + H+, 5), 329 (10),
225 (85), 105 (100), 77 (30), 55 (45); HRMS calcd for C23H23O3
(M + H+) 347.1642, found 347.1666.
cis-3-Benzoyloxy-4-hydroxytetrahydrofuran (20).7f,g White solid:
mp 82−83 °C (lit.7f mp 80−81 °C); H NMR (400 MHz, CDCl3)
1
δ 8.07 (d, J = 7.1 Hz, 2H), 7.60 (t, J = 7.3 Hz, 1H), 7.47 (dd, J = 7.3,
7.1 Hz, 2H), 5.40 (ddd, J = 5.9, 5.6, 4.2 Hz, 1H), 4.59 (ddd, J = 5.9,
5.6, 5.4 Hz, 1H), 4.19 (dd, J = 10.3, 5.9 Hz, 1H), 4.06 (dd, J = 9.4,
5.9 Hz, 1H), 4.01 (dd, J = 10.3, 4.2 Hz, 1H), 3.81 (dd, J = 9.4, 5.4 Hz,
1H), 2.24 (br s, 1H); 13C NMR (100 MHz, CDCl3) δ 166.3, 133.5,
129.8 (2), 128.5 (3), 74.3, 72.4, 71.2, 70.6; IR (neat) 3424, 2953, 1715,
1269, 1117 cm−1; MS m/z (rel intensity) 208 (M+, 5), 165 (15), 122
(85), 105 (100), 77 (75), 51 (25); HRMS calcd for C11H12O4 (M+)
208.0736, found 208.0726.
syn-2-Benzoyloxy-1,2-diphenylethanol (27).10 White solid: mp
144−145 °C (lit.10 mp 146−148 °C); 1H NMR (400 MHz, CDCl3) δ
8.10 (dd, J = 7.3, 1.2 Hz, 2H), 7.57 (td, J = 7.3, 1.2 Hz, 1H), 7.45
(dd, J = 7.3, 1.2 Hz, 2H), 7.30−7.15 (m, 10H), 6.11 (d, J = 7.3 Hz,
1H), 5.07 (dd, J = 7.3, 2.4 Hz, 1H), 2.73 (br s, 1H); 13C NMR
(100 MHz, CDCl3) δ 165.7, 139.0, 136.8, 133.2, 129.7, 128.4 (2),
128.2 (2), 128.2 (2), 128.1 (2), 128.1 (2), 127.2 (2), 127.1 (2), 80.5,
77.3; IR (neat) 3480, 3032, 1692, 1277, 1117 cm−1; MS m/z (rel
intensity) 319 (M + H+, 15), 197 (30), 154 (100), 136 (70), 105 (60),
77 (25); HRMS calcd for C21H19O3 (M + H+) 319.1329, found
319.1338.
cis-3-Hydroxyl-2-tetralinyl Benzoate (21).7f Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 2H), 7.55 (t, J =
7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.25−7.00 (m, 4H), 5.54−5.50
(m, 1H), 4.38−4.35 (m, 1H), 3.31−3.07 (m, 4H), 2.36 (br s, 1H); 13C
NMR (100 MHz, CDCl3) δ 166.6, 133.2, 132.8, 132.4, 130.0, 129.7
(2), 129.2, 129.0, 128.4 (2), 126.4, 126.3, 73.0, 67.9, 34.8, 31.7; IR
(neat) 3422, 2930, 1713, 1271, 1113 cm−1; MS m/z (rel intensity) 269
(M + H+, 45), 165 (10), 147 (70), 105 (85), 69 (100); HRMS calcd
for C17H17O3 (M + H+) 269.1172, found 269.1173.
syn-Diisopropyl 2-Benzoyloxytartrate (28). White solid: mp 67−
68 °C; 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.8 Hz, 2H), 7.58
(t, J = 7.4 Hz, 1H), 7.44 (dd, J = 7.8, 7.4 Hz, 2H), 5.65 (d, J = 2.2 Hz,
1H), 5.16 (sep, J = 6.3 Hz, 1H), 5.09 (sep, J = 6.3 Hz, 1H), 4.83 (d, J =
2.2 Hz, 1H), 3.42 (br s, 1H), 1.31 (d, J = 6.3 Hz, 3H), 1.29 (d, J =
6.3 Hz, 3H), 1.26 (d, J = 6.3 Hz, 3H), 1.08 (d, J = 6.3 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 170.5, 166.0, 165.2, 133.5, 129.9 (2),
128.7, 128.4 (2), 73.5, 70.7, 70.7, 70.1, 21.7, 21.6, 21.5, 21.4; IR (neat)
3451, 2982, 1717, 1227, 1099 cm−1; MS m/z (rel intensity) 339
(M + H+, 50), 297 (15), 255 (20), 154 (10), 105 (100), 77 (10);
HRMS calcd for C17H23O7 (M + H+) 339.1438, found 339.1447.
cis-2-Hydroxycyclooct-5-enyl Benzoate (22). Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.10−8.06 (m, 2H), 7.61−7.56 (m, 1H),
7.49−7.44 (m, 2H), 5.85−5.70 (m, 2H), 5.29 (dd, J = 7.5, 3.5 Hz,
1H), 4.20−4.10 (m, 1H), 3.04 (br s, 1H), 2.75−2.50 (m, 2H), 2.20−
1.95 (m, 3H), 1.95−1.70 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
167.2, 133.2, 130.7, 130.0, 130.0, 129.7 (2), 128.4 (2), 81.3, 73.6,
33.5, 30.3, 22.0, 21.6; IR (neat) 3402, 2934, 1694, 1269, 1113 cm−1;
MS m/z (rel intensity) 247 (M + H+, 45), 154 (10), 123 (35), 105
(100), 77 (20); HRMS calcd for C15H19O3 (M + H+) 247.1329, found
247.1329.
rac-2-Benzyl-3-hydroxypropyl Benzoate (29).11 Colorless oil: H
1
NMR (400 MHz, CDCl3) δ 8.05−8.02 (m, 2H), 7.60−7.55 (m, 1H),
7.47−7.43 (m, 2H), 7.33−7.19 (m, 5H), 4.45 (dd, J = 11.2, 4.4 Hz,
1H), 4.33 (dd, J = 11.2, 6.1 Hz, 1H), 3.69 (dd, J = 11.2, 4.6 Hz, 1H),
3.60 (dd, J = 11.2, 6.3 Hz, 1H), 3.20 (br s, 1H), 2.78 (dd, J = 13.7, 7.3
Hz, 1H), 2.73 (dd, J = 13.7, 7.7 Hz, 1H), 2.32−2.20 (m, 1H); 13C
NMR (100 MHz, CDCl3) δ 167.1, 139.3, 133.1, 129.9, 129.6 (2),
129.0 (2), 128.5 (2), 128.4 (2), 126.2, 64.2, 62.0, 42.7, 34.4; IR (neat)
3483, 3063, 1717, 1271, 1113 cm−1; MS m/z (rel intensity) 271 (M +
H+, 60), 253 (35), 154 (45), 105 (100), 91 (50); HRMS calcd for
C17H19O3 (M + H+) 271.1329, found 271.1336.
cis-1-hydroxy-2,3-dihydro-1H-inden-2-yl Benzoate (23a).8 1H
NMR (400 MHz, CDCl3) δ 8.08−8.01 (m, 1H), 7.57−7.40 (m,
1H), 7.40−7.20 (m, 2H), 6.20 (d, J = 5.1 Hz, 1H), 4.72 (q, J = 5.8 Hz,
1H), 3.30−3.00 (m, 2H), 2.84 (br s, 1H); 13C NMR (100 MHz,
CDCl3) δ 166.4, 141.1, 138.2, 133.0, 129.7, 129.7 (2), 129.4, 128.3
(2), 127.1, 126.1, 124.9, 78.0, 72.9, 38.6; IR (neat) 3358, 3063, 1717,
1271, 1099 cm−1; MS m/z (rel intensity) 255 (M + H+, 5), 237 (50),
154 (30), 105 (95), 77 (35), 55 (60); HRMS calcd for C16H15O3 (M +
H+) 255.1016, found 255.1008.
2-Hydroxy-2,3-dihydro-1H-inden-1-yl Benzoate (23b).8 1H NMR
(400 MHz, CDCl3) δ 7.98−7.95 (m, 1H), 7.57−7.40 (m, 1H), 7.40−
7.20 (m, 2H), 5.67−5.62 (m, 1H), 5.28 (d, J = 5.1 Hz, 1H), 3.30−3.00
rac-2-Diethyl-3-hydroxybutyl Benzoate (30). Colorless oil: 1H
NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.3 Hz, 2H), 7.59−7.54 (m,
1H), 7.47−7.42 (m, 2H), 4.22 (s, 2H), 3.41 (s, 2H), 2.47 (br s, 1H),
758
dx.doi.org/10.1021/jo202136a | J. Org. Chem. 2012, 77, 754−759

The Journal of Organic Chemistry
Note
1.50−1.25 (m, 4H), 0.89 (t, J = 7.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 167.1, 133.1, 130.0, 129.6 (2), 128.4 (2), 66.3, 64.1, 41.5,
22.3 (2), 7.0 (2); IR (neat) 3420, 2965, 1699, 1269, 1113 cm−1; MS
m/z (rel intensity) 237 (M + H+, 95), 219 (15), 123 (65), 105 (100),
77 (15); HRMS calcd for C14H21O3 (M + H+) 237.1485, found
237.1476.
Angew. Chem., Int. Ed. 2010, 49, 262−310. (h) Yoshida, K.; Furuta, T.;
Kawabata, T. Angew. Chem., Int. Ed. 2011, 123, 4990−4994.
(2) (a) Nishino, S.; Ishido, Y. Carbohydr. Res. 1986, 155, 161−174.
(b) Kurahashi, T.; Mizutani, T.; Yoshida, J. J. Chem. Soc., Perkin Trans.
1 1999, 465−474. (c) Kurahashi, T.; Mizutani, T.; Yoshida, J.
Tetrahedron 2002, 58, 8669−8677. (d) Griswold, K. S.; Miller, S. J.
Tetrahedron 2003, 59, 8869−8875. (e) Kawabata, T.; Muramatsu, W.;
Nishio, T.; Shibata, T.; Schedel, H. J. Am. Chem. Soc. 2007, 129,
12890−12895. (f) Kawabata, T.; Muramatsu, W.; Nishio, T.; Shibata,
T.; Uruno, Y.; Stragies, R. Synthesis 2008, 747−753. (g) Demizu, Y.;
Kubo, Y.; Miyoshi, H.; Maki, T.; Matsumura, Y.; Moriyama, N.;
Onomura, O. Org. Lett. 2008, 10, 5075−5077. (h) Ueda, Y.;
Muramatsu, W.; Mishiro, K.; Furuta, T.; Kawabata, T. J. Org. Chem.
2009, 74, 8802−8805. (i) Dhiman, R. S.; Kluger, R. Org. Biomol. Chem.
2010, 8, 2006−2008. (j) Lee, D.; Taylor, M. S. J. Am. Chem. Soc. 2011,
133, 3724−3727.
rac-2-Hydroxy-2-phenylethyl Benzoate (31).12 White solid: mp
67−68 °C (lit.12 mp 65−67 °C); H NMR (400 MHz, CDCl3) δ
1
8.06−8.01 (m, 2H), 7.60−7.50 (m, 1H), 7.50−7.28 (m, 7H), 5.07 (dd,
J = 8.0, 3.7 Hz, 1H), 4.49 (dd, J = 11.5, 3.7 Hz, 1H), 4.40 (dd, J = 11.5,
3.7 Hz, 1H), 2.96 (br s, 1H); 13C NMR (100 MHz, CDCl3) δ 166.7,
139.9, 133.1, 129.7, 129.6 (2), 128.5 (2), 128.4 (2), 128.1, 126.1 (2),
72.4, 69.7; IR (neat) 3294, 2913, 1717, 1263, 1090 cm−1; MS m/z (rel
intensity) 243 (M + H+, 20), 154 (30), 137 (30), 105 (100), 77 (25),
69 (10); HRMS calcd for C15H15O3 (M + H+) 243.1016, found
243.1035.
General Procedure for Asymmetric Benzoylation of 1,2-
Diols in Water. CuCl2 (26.9 mg, 0.20 mmol) and (R,R)-PhBox
(100.3 mg, 0.30 mmol) were mixed in purified water at room
temperature for 1 h under Ar atmosphere. Then, meso-1,2-cyclo-
octanediol (144 mg, 1.0 mmol) and Me2SnCl2 (22.0 mg, 0.10 mmol)
were added. After the suspension was stirred for 10 min, K2CO3
(138 mg, 1.0 mmol), DMT-MM (including 15.6% water, 393 mg,
1.2 mmol), 4-dimethylaminopyridine (12.2 mg, 0.10 mmol), and
benzoyl chloride (139 mL, 1.2 mmol) were added to a suspension at
room temperature under Ar atmosphere. After stirring for 5 days, the
reaction mixture was quenched with saturated aqueous NH4Cl and
extracted with ethyl acetate. The organic layer was washed with water
and brine, dried with MgSO4, filtrated, and concentrated in vacuo. The
residue was purified by SiO2 column chromatography (n-hexane/ethyl
acetate = 10/1) to give cis-2-hydroxycyclooctyl benzoate (1S,2R)-1
(146.5 mg, 59%, 60% ee) as colorless oil.
(3) (a) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous Media;
Wiley: New York, 1997. (b) Grieco, P., Ed.; Organic Reactions in
Water; Blackie Academic & Professional: London, 1998. (c) Knochel,
P.; Houk, K. N.; Keddler, H., Eds.; Modern Solvents In Organic
Synthesis; Springer: Berlin, 1999; Topics in Current Chemistry, Vol
206. (d) Li, C.-J. Chem. Rev. 1993, 93, 2023−2035. (e) Kobayashi, S.
Adv. Synth. Catal. 2002, 344, 219. (f) Sinou, D. Adv. Synth. Catal.
2002, 344, 221−237.
(4) For great method for acylation in water, see: (a) Cameron, L. L.;
Wang, S. C.; Kluger, R. J. Am. Chem. Soc. 2004, 126, 10721−10726.
(b) Nakatsuji, H.; Morita, J.; Misaki, T.; Tanabe, Y. Adv. Synth. Catal.
2006, 348, 2057−2062.
(5) For examples, see: (a) Kaminski, Z. J.; Paneth, P.; Rudzinski, J.
J. Org. Chem. 1998, 63, 4248−4255. (b) Kunishima, M.; Kawachi, C.;
Iwasaki, F.; Terao, K.; Tani, S. Tetrahedron Lett. 1999, 40, 5327−5330.
(c) Kunishima, M.; Morita, J.; Kawachi, C.; Iwasaki, F.; Terao, K.;
Tani, S. Synlett 1999, 1255−1256. (d) Kunishima, M.; Kawachi, C.;
Morita, J.; Terao, K.; Iwasaki, F.; Tani, S. Tetrahedron 1999, 55,
13159−13170. (e) Falchi, A.; Giacomelli, G.; Porcheddu, A.; Taddei,
M. Synlett 2000, 275−277. (f) Demarcus, M.; Ganadu, M. J.; Mura,
G. M.; Porcheddu, A.; Quaranta, L.; Reginato, G.; Taddei, M. J. Org.
Chem. 2001, 66, 697. (g) Meloni, M. M.; Taddei, M. Org. Lett. 2001,
3, 337.
(1S,2R)-2-Hydroxycyclooctyl Benzoate (1S,2R)-1.7f HPLC: OJ-H
column, n-hexane/isopropanol = 98:2, wavelength = 254 nm, flow
rate = 1.0 mL/min, retention time = 13.7 min (major), 16.9 min.
7f
25
20
[α]D = +5.9 (60% ee, c = 1.00, CHCl3), lit. [α]D = +8 (77% ee,
c = 0.90, CH2Cl2).
(1S,2R)-2-Benzoyloxy-1,2-diphenylethanol (1S,2R)-25.7b HPLC: OJ
column, n-hexane/isopropanol = 5:1, wavelength = 254 nm, flow
rate = 1.0 mL/min, retention time = 10.2 min, 15.7 min (major). 99%
(6) (R,R)-2,2′-Isopropylidene-bis(4-phenyl-2-oxazoline).
ee. [α]D = −36.2 (c = 1.00, CHCl3), lit.7b [α]D = −35.3 (94% ee,
25
24
(7) (a) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem.
Soc. 1997, 119, 3169−3170. (b) Matsumura, Y.; Maki, T.; Murakami,
S.; Onomura, O. J. Am. Chem. Soc. 2003, 125, 2052−2053. (c) Mizuta,
S.; Sadamori, M.; Fujimoto, T.; Yamamoto, I. Angew. Chem., Int. Ed.
2003, 42, 3383−3385. (d) Mazet, C.; Kohler, V.; Pfaltz, A. Angew.
Chem., Int. Ed. 2005, 44, 4888−4891. (e) Nakamura, D.; Kakiuchi, K.;
c = 1.00, CHCl3).
ASSOCIATED CONTENT
■
S
* Supporting Information
Copies of spectra for new compounds. This material is available
free of charge via the Internet at http://pubs.acs.org.
Koga, K.; Shirai, R. Org. Lett. 2006, 8, 6139−6142. (f) Kundig, E. P.;
̈
Garcia, A. E.; Lomberget, T.; Garcia, P. P.; Romanens, P. Chem.
Commun. 2008, 3519−3521. (g) Recuero, V.; Brieva, R.; Gotor, V.
Tetrahedron: Asymmetry 2008, 19, 1684−1688.
AUTHOR INFORMATION
■
(8) Mitsunobu, O.; Kimura, J.; Iiizumi, K.; Yanagisa, N. Bull. Chem.
Soc. Jpn. 1976, 49, 510−513.
Corresponding Author
*E-mail: muramatu@nagasaki-u.ac.jp.
(9) Bredikhin, A. A.; Bredikhina, Z. A.; Zakharychev, D. V.;
Konoshenko, L. V. Tetrahedron: Asymmetry 2007, 18, 1964−1970.
(10) Gissibl, A.; Finn, M. G.; Reiser, O. Org. Lett. 2005, 7, 2325−
2328.
ACKNOWLEDGMENTS
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This research was funded by Special Coordination Funds for
Promoting Science and Technology from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
(11) Trost, B. M.; Malhotra, S.; Mino, T.; Rajapaksa, N. S. Chem.
Eur. J. 2008, 14, 7648−7657.
(12) Ciuffreda, P.; Alessandrini, L.; Terraneo, G.; Santaniello, E.
Tetrahedron: Asymmetry 2003, 14, 3197−3201.
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