Ring-opening reactions of epoxides catalyzed by molybdenum(VI) dichloride dioxide

Article abstract of DOI:10.1055/s-2008-1032163

Transformation of epoxides to β-alkoxy alcohols, acetonides, and α-alkoxy ketones is achieved by using molybdenum(VI) dichloride dioxide (MoO₂Cl₂) as a catalyst. Alcohol, aldehyde, oxime, tosyl, and tert-butyldimethylsilyl functional groups are tolerated during the methanolysis and acetonidation of the functionalized epoxides. No polymerization product is observed with any of the epoxides. Direct conversion of epoxides devoid of sensitive functional groups into the corresponding α-methoxy ketone is achieved in a single step by using the MoO₂Cl ₂/Oxone system. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1032163

PAPER
807
Ring-Opening Reactions of Epoxides Catalyzed by Molybdenum(VI)
Dichloride Dioxide
R
ing-Opening Re
a
a
ctions of
E
n
poxides dasamy Jeyakumar, Dillip Kumar Chand*
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India
Fax +91(44)22574202; E-mail: dillip@iitm.ac.in
Received 21 November 2007; revised 4 December 2007
Abstract: Transformation of epoxides to b-alkoxy alcohols, ace-
O
O
O
HO
OR
tonides, and a-alkoxy ketones is achieved by using molybde-
num(VI) dichloride dioxide (MoO2Cl2) as a catalyst. Alcohol,
aldehyde, oxime, tosyl, and tert-butyldimethylsilyl functional
groups are tolerated during the methanolysis and acetonidation of
the functionalized epoxides. No polymerization product is observed
with any of the epoxides. Direct conversion of epoxides devoid of
sensitive functional groups into the corresponding a-methoxy ke-
tone is achieved in a single step by using the MoO2Cl2/Oxone sys-
tem.
O
OR
Scheme 1
Key words: molybdenum, catalyst, epoxides, nucleophiles, ring
opening
groups present in the substrate during the ring-opening re-
action has not been explored.
In our preliminary experiments, we studied the ring-open-
ing reaction of styrene oxide (1) by using various alcohols
(i.e., primary, secondary, and tertiary alcohols), acetic ac-
id, and water with a catalytic amount of MoO2Cl2. The nu-
cleophile attacks at the a-position of the epoxide at room
temperature and provide the regioselective products 2a–f
in 79–95% yields (Table 1). We have extended the use of
MoO2Cl2 in the methanolysis of several other epoxides
and the results are summarized in Table 3.
Epoxides are widely distributed in nature and used as ver-
satile intermediates in organic synthesis.1 Epoxides react
with various reactants such as electrophiles, nucleophiles,
acids, bases, and redox agents.2 Among the various trans-
formations of epoxides, ring-opening reactions with a va-
riety of nucleophiles containing oxygen (e.g., alcohol,
acids, H2O, and acetone), nitrogen (e.g., amines and
azides), and sulfur (e.g., thiols) are in demand, which usu-
ally provide 1,2-bifunctional compounds.3 Generally, the
oxygen-containing nucleophiles behave as poor nucleo-
philic reagents in substitution processes, thus they require
strongly acidic or basic conditions.4
A symmetrical epoxide, i.e. cyclohexene oxide (3) is con-
verted into 2-methoxycyclohexanol (16) at room temper-
ature in 91% yield. In the case of unsymmetrical epoxides
4–15 we observed the nucleophile attack at the b-position
of the epoxides, which gives regioselective products 17–
28. Since the reaction of some of the epoxides 4–9 and
12–15 take extended periods (10–24 h) to go to comple-
Recently,
molybdenum(VI)
dichloride
dioxide
(MoO2Cl2) has been used as an efficient catalyst for sev-
eral organic transformations.5 We have also recently de-
veloped MoO2Cl2 as a mild and selective catalyst for the
oxidation of sulfides and alcohols.6 In this article we wish
to report further applications of MoO2Cl2 as a catalyst for
Table 1 Ring-Opening Reaction of Styrene Oxide (1) Using Vari-
the transformation of epoxides to b-alkoxy alcohols, ace- ous Alcohols
tonides, and a-alkoxy ketones (Scheme 1).
MoO2Cl2 (5 mol%)
ROH (5 mL)
OR
O
OH
Epoxide ring-opening reactions with alcohols (i.e.,
Ph
N2, r.t., 2 h
MeOH, i-PrOH, t-BuOH) can be achieved with various
Ph
catalysts.7 However, most of the reported methods suffer
1
2a–f
from the use of strongly acidic catalysts, extended reac-
tion times, low regioselectivity, unsatisfactory yields, and
R
Product
2a
Isolated yield (%)
the formation of side products due to rearrangement or po-
Me
95
92
83
79
93
89
lymerization of the epoxides.4,8 Furthermore, the compat-
Et
2b
ibility of sensitive functional groups such as alcohol,
aldehyde, oxime, tosyl, and tert-butyldimethylsilyl
i-Pr
t-Bu
Ac
H
2c
2d
SYNTHESIS 2008, No. 5, pp 0807–0819
x
x
.
x
x
.2
0
0
8
2e
Advanced online publication: 08.02.2008
DOI: 10.1055/s-2008-1032163; Art ID: Z26807SS
© Georg Thieme Verlag Stuttgart · New York
2f

808
K. Jeyakumar, D. K. Chand
PAPER
strate, the product was completely deprotected to provide
19 in quantitative yield (Table 2).
The 2,2-dimethyl-1,3-dioxolane (acetonide) group is the
most widely used protecting group for vicinal diols; they
are usually prepared from the condensation of diols with
acetone or 2,2-dimethoxypropane, under acidic condi-
tions.12 However the diols themselves are typically pre-
pared via osmium-catalyzed dihydroxylation of the
corresponding alkene or hydration of the epoxide precur-
sors, respectively.14
Figure 1
Table 2 Ring-Opening Reaction of Epoxides Containing the tert-
Butyldimethylsilyl Group
O
OMe
+
O
O
OMe
The direct conversion of epoxides into the corresponding
acetonides has previously been reported with a variety of
Lewis acid catalysts including BF3·OEt2, SnCl2, SnCl4,
anhyd CuSO4, TiCl4, TiCl3(OTf), TiO(OCOCF3), RuCl3,
K10-montmorillonite, and bismuth(III) salts.15 However,
many of these catalysts are rather strong Lewis acids and
they are incompatible with other functional or protecting
groups.
O
OH
OH
conditions
OTBS
OTBS
OH
15
28
19
Conditions
Time
Isolated yield (%)
28
64
0
19
20
97
Initially we studied the reaction of styrene oxide (1) with
various ketones, which gives the corresponding acetonide
derivatives 29 and 30 at room temperature in 90–91%
yields (Table 4, entries 1 and 2). Furthermore, we have
studied other functional groups containing epoxides and
the results are summarized in Table 4.
MoO2Cl2, MeOH, N2, 50 °C
NaOMe, MeOH, r.t.
5 h
5 min
tion at room temperature, we have performed it at 50 °C,
at which temperature the reaction is complete within 1–5
hours.
For the epoxides 4–9 and 12–15 the reaction was carried
out at 50 °C, since the reaction for these epoxides takes
longer to go to completion at room temperature. Most
functional groups, such as alcohol, aldehyde, oxime, allyl,
propargyl, benzyl, and tosyl, are compatible under the
conditions employed in this study. In case of tert-bu-
tyldimethylsilyl-protected epoxide 15, we observed 5% of
the deprotected product (i.e., 34) together with the major
product 43.
The potential benefit of this methodology is the tolerance
of some sensitive functional groups during the ring-open-
ing reactions as mentioned here. The inbuilt alcoholic
functionality within the substrate (phenol 6 and benzyl al-
cohol 7) is unreactive towards epoxide ring opening. Dur-
ing such ring-opening reactions, we have not observed
any self-ring-opening polymerization. We also obtained
the crystal structure (Figure 1) for the compound 19,
which clearly shows the formation of a regioselective
product.9 The epoxide with the aldehyde functionality 8
gives only the ring-opening product 21 under the present
Lewis acidic conditions. We did not observe the conver-
sion of the aldehyde into the corresponding acetal with
this substrate which is a feasible reaction.10 The reactive
oxime functional group, which generally undergoes a
cleavage or rearrangement,11 is stable under the reaction
conditions employed in the present study as seen in case
of the conversion of 9 into 22 using MoO2Cl2. Allyl-, pro-
pargyl-, benzyl-, and tosyl-protected epoxides 10–13 are
highly stable and gave the corresponding methanolysis
products 23–26 in good yields.
a-Alkoxy ketones are highly important building blocks in
many syntheses and also constitute a class of naturally oc-
curring compounds.16 These compounds have previously
been prepared by indirect methods, which include the ad-
dition of organocuprates to a-methoxyenones, photolysis
of a-chloro ketones in methanol, oxidation of enol acetate
with methyl hypofluorite, oxidation of silyl enol ethers
with iodosobenzene/boron trifluoride–diethyl ether com-
plex in methanol, reaction of a-hydroxy ketones with
alkyl iodides, and anodic oxidation of enol acetate in
methanol.17 However, these methods require multiple ox-
idation procedures or the use of exotic reaction condi-
tions.
Therefore, the introduction of new methods for the syn-
thesis of a-alkoxy ketones under mild conditions, are still
in demand and are important in synthetic organic chemis-
try. Here we wish to report a one-pot synthesis of a-meth-
oxy ketones from some simple epoxides by using the
MoO2Cl2/Oxone (KHSO5) system in methanol. In our
preliminary study we tested the oxidation of cyclohexene
oxide (3) in various alcohols by using 15 mol% of
MoO2Cl2 with 1.2 equivalents of Oxone under reflux con-
ditions (Table 5); 2-alkoxycyclohexanones 44a–c are ob-
served in 72–80% yields.
tert-Butyldimethylsilyl-protected organic compounds
have versatile applications in organic synthesis. However,
such organic substrates are prone to undergo cleavage un-
der strongly acidic/basic conditions.12,13 Since such sys-
tems (i.e., tert-butyldimethylsilyl-protected epoxides)
have not been previously studied, we have analyzed the
epoxide 15 containing highly labile tert-butyldimethylsi-
lyl group (Table 2), the expected product 28 was obtained
in 64% yield. When the usual method of methanolysis by
using sodium methoxide was employed for the same sub-
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

PAPER
Ring-Opening Reactions of Epoxides
809
Table 3 Methanolysis of Various Epoxides to b-Alkoxy Alcohols Using MoO2Cl2 as Catalysta
Entry
1
Substrate
Product
Time (h)
1
Yieldb (%)
OMe
O
OH
95c
91c
57
1
2a
16
OH
O
2
3
1
1
OMe
3
OMe
O
OH
MeO
MeO
OMe
O
OMe
O
4
17
OH
O
OMe
4
5
1
92
82
5
18
OH
O
O
O
OMe
1.5
HO
HO
6
19
OH
O
O
O
OMe
6
7
1
89
72
OH
OH
7
20
OH
O
O
O
OMe
1.5
OHC
OHC
8
21
OH
O
O
O
OMe
8
9
5
1
62
N
N
HO
HO
9
22
OH
O
72c
O
O
OMe
OMe
10
11
23
24
OH
O
79c
68
78
O
10
11
12
1
1
3
O
OH
OH
O
BnO
BnO
OMe
OMe
12
25
O
TsO
TsO
13
26
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

810
K. Jeyakumar, D. K. Chand
PAPER
Table 3 Methanolysis of Various Epoxides to b-Alkoxy Alcohols Using MoO2Cl2 as Catalysta (continued)
Entry
13
Substrate
Product
Time (h)
2
Yieldb (%)
OH
O
n-C5H11
73
n-C5H11
OMe
14
27
OH
O
O
OMe
O
14
5
64
TBSO
TBSO
15
28
a Reaction conditions: epoxide (3 mmol), MeOH (5 mL), MoO2Cl2 (5 mol%), N2, 50 °C (unless otherwise indicated).
b Isolated yield.
c Reactions proceed at r.t.
Table 4 Conversion of Various Epoxides into the Corresponding Acetonides Using MoO2Cl2 as Catalysta
Entry
Substrate
Product
Time (h)
2
Yieldb (%)
O
O
O
O
O
1
91c
1
29
Et
Et
O
2
2
90c
1
30
31
O
O
3
4
1
1
81c
92
O
3
O
O
O
MeO
MeO
OMe
O
OMe
O
4
32
O
O
O
5
6
1
91
92
5
33
O
O
O
O
O
1.5
HO
HO
6
34
O
O
O
O
O
7
1
81
OH
OH
7
35
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

PAPER
Ring-Opening Reactions of Epoxides
811
Table 4 Conversion of Various Epoxides into the Corresponding Acetonides Using MoO2Cl2 as Catalysta (continued)
Entry
8
Substrate
Product
Time (h)
1.5
Yieldb (%)
O
O
O
O
O
87
OHC
OHC
8
36
O
O
O
O
O
9
5
52
N
HO
N
HO
9
37
38
39
O
O
O
10
11
12
13
14
1
1
1
3
3
92c
82c
88
O
O
10
11
O
O
O
O
O
O
O
O
BnO
BnO
O
12
40
O
TsO
78
TsO
O
13
41
O
O
n-C5H11
89
n-C5H11
O
14
42
O
O
O
O
15
1.5
85d
O
TBSO
TBSO
15
43
a Reaction conditions: epoxide (3 mmol), R2CO (5 mL), MoO2Cl2 (5 mol%), N2, 50 °C (unless otherwise indicated).
b Isolated yield.
c Reactions proceed at r.t.
d 34 is observed in 5%.
Furthermore we have studied the oxidation of various ep- compound 15, which is a tert-butyldimethylsilyl-protect-
oxides and the results are summarized in Table 6. In the ed phenolic substrate, ring opening and deprotection oc-
case of styrene oxide (1), methanolysis provides a primary curred to give 19 as the major product. Compound 7,
alcohol which does not stop at the aldehyde stage. Instead which has an activated benzylic alcohol, gave a mixture of
the corresponding ester 45 was obtained as the major products at room temperature, from the mixture 19, 21,
product.18 Epoxides 4 and 5 are oxidized to the corre- and 48 could be isolated in low yields. However, the same
sponding methoxy ketones 46 and 47 in good yields. The reaction when carried out under reflux conditions without
other epoxides which contain sensitive functional groups Oxone in acetonitrile–methanol mixture (1:1), provides
6–9 and 15 are not tolerated under reflux conditions. For 21 as the sole product in 90% yield (Scheme 2).
such substrates, we carried out the reactions at room tem-
We also observed that in the case of aldehyde-functional-
perature. In case of the phenolic compound 6 only the cor-
ized substrate 8, the major product at room temperature
responding ring-opened product 19 was observed. For the
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

812
K. Jeyakumar, D. K. Chand
PAPER
OH
Table 5 Oxidation of Cyclohexene Oxide (3) in Various Alcohols
Using MoO2Cl2 with Oxone
O
MoO2Cl2
(15 mol%), O2
O
OMe
O
MoO2Cl2 (15 mol%)
O
MeCN–MeOH
(5 mL)
Oxone (1.2 equiv)
O
ROH (5 mL), reflux
OR
reflux, 3 h
O
OH
7
21 90%
3
44a–c
Scheme 2
R
Product
44a
Isolated yield (%)
phenols when treated with Oxone in methanol.18 The
oxime-functionalized substrate 9 gave the aldehyde 21 as
the major product with 1.1 equivalents of Oxone, where
the oxime is deprotected by Oxone.19 The allyl compound
10 gave the expected product 49 where the double bond
remained intact. Propargyl, benzyl, and tosyl functional
groups are also stable and the expected compounds 50–52
are formed as the major product.
Me
Et
80
75
72
44b
i-Pr
44c
was the phenol 19. It has been reported recently that elec-
tron-rich aldehydes usually provides the corresponding
a
Table 6 Oxidation of Various Epoxides to the Corresponding a-Methoxy Ketones Using MoO2Cl2
Entry
Substrate
Product
Time (h)
9
Yieldb (%)
59c
OMe
O
O
OMe
1
1
45
O
O
2
3
2
72
50
OMe
3
44a
OMe
O
O
2.5
MeO
MeO
OMe
O
OMe
O
4
46
O
O
OMe
4
5
2
2
85
5
47
OH
O
O
O
OMe
76d
HO
HO
6
19
O
O
O
O
OMe
6
7
18
14
20d,e
OH
O
7
48
OH
O
O
O
OMe
58d
OHC
HO
8
19
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

PAPER
Ring-Opening Reactions of Epoxides
813
Table 6 Oxidation of Various Epoxides to the Corresponding a-Methoxy Ketones Using MoO2Cl2a (continued)
Entry
8
Substrate
Product
Time (h)
Yieldb (%)
OH
O
O
O
O
OMe
6
71d,f
N
HO
O
9
21
O
O
9
2
80
72
65
70
78
O
OMe
10
11
49
50
O
O
10
11
12
13
1.5
3
O
O
OMe
O
O
O
O
BnO
BnO
OMe
OMe
12
51
TsO
3
TsO
13
52
O
O
n-C5H11
4.5
n-C5H11
OMe
14
53
OH
O
O
OMe
O
14
9
71d
TBSO
HO
15
19
a Reaction conditions: epoxide (1 mmol), MeOH (3 mL), Oxone (1.2 equiv), MoO2Cl2 (15 mol%), stirred, reflux.
b Isolated yield.
c Oxone (2 equiv) used.
d Reaction carried out at r.t.
e 19 and 21 were isolated in 15% and 20% yields, respectively.
f 19 also observed in <10%.
Cl
The proposed mechanism for epoxide ring opening is
O
S
O
S
Mo
Cl
shown in Scheme 3. It is well known that MoO2Cl2 can
bind with various kinds of oxygen donors to give the cor-
responding molybdenum addition compounds.20 The first
step presumably involves the coordination of epoxide to
the vacant sites of MoO2Cl2. In the next step possibly the
nucleophile attacks the epoxide, which gives the desired
products.
Nu
OH
Nu
S = Solvent
O
Cl
O
O
O
Mo
Cl
The solvents were dried using literature methods21 and reactions are
performed under an N2 atmosphere. The products are characterized
by 1H and 13C NMR (Bruker 400 MHz NMR spectrometer), IR (Jas-
co FT/IR 660 plus), and melting points (Toshnival-India melting
point apparatus); 1H and 13C NMR used TMS as a reference. Mass
spectra were recorded on Q-Tof-Mass spectrometer equipped with
a standard electrospray source (Q-Tof micro hybrid quadrupole
TOF mass spectrometer).
O
Scheme 3
recorded with those in the literature. For such compounds selected
data (IR and 1H NMR) are provided. For some of the reported com-
pounds, no analytical data is available. For such compounds and all
other new compounds complete analytical data is given here.
The catalyst MoO2Cl2, epoxides 1, 3, 5, 10, 11, 12, and 14 were ac-
quired from Aldrich. Other epoxides 6, 7, 8, 13, and 15 were pre-
pared using literature procedures. Two epoxides 4 and 9 were
synthesized in this work and the analytical data are given in this sec-
tion. For known compounds, we have compared the analytical data
2-(3,4-Dimethoxybenzyl)oxirane (4)
Epoxide 422g was prepared by an alternative route.
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

814
K. Jeyakumar, D. K. Chand
PAPER
A mixture of 4-allyl-1,2-dimethoxybenzene (1.78 g, 10 mmol) and
MCPBA (77%, 3.5 g) in CH2Cl2 (30 mL) was stirred at r.t. for 5 h.
The resultant mixture was filtered and the filtrate was washed with
NaHCO3 and extracted with CH2Cl2. The combined CH2Cl2 ex-
tracts were evaporated under reduced pressure. The crude product
was subjected to column chromatography to give a yellowish liquid;
yield: 1.25 g (62%).
(dd, J = 11.6, 5.7 Hz, 1 H), 3.36 (m, 1 H), 2.92 (t, J = 4.4 Hz, 1 H),
2.77 (dd, J = 4.6, 2.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 159.8, 149.7, 128.5, 125.1, 114.9,
68.7, 50.0, 44.7.
HRMS: m/z [M + H] calcd for C10H12NO3: 194.0817; found:
194.0819.
IR (neat): 2890, 1512, 1260 cm–1.
Anal. Calcd for C10H11NO3: C, 62.17; H, 5.74; N, 7.25. Found: C,
62.01; H, 5.60; N, 7.10.
1H NMR (400 MHz, CDCl3): d = 6.83–6.78 (m, 3 H), 3.88 (s, 3 H),
3.86 (s, 3 H), 3.14 (m, 1 H), 2.80 (m, 3 H), 2.54 (dd, J = 4.9, 2.6 Hz,
1 H).
13C NMR (100 MHz, CDCl3): d = 148.9, 147.8, 129.7, 120.9, 112.2,
111.2, 55.9, 55.8, 52.6, 46.8, 38.3.
HRMS: m/z [M + H]+ calcd for C11H15O3: 195.1021; found:
195.1026.
2-(Tosyloxymethyl)oxirane (13)
Prepared by using the literature method22n as a colorless liquid.
IR (neat): 1596 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.80 (d, J = 8.8 Hz, 2 H), 7.35 (d,
J = 8.8 Hz, 2 H), 4.22–4.28 (dd, J = 11.0, 2.9 Hz, 1 H), 3.91–3.96
(dd, J = 11.6, 5.7 Hz, 1 H), 3.16–3.21 (m, 1 H), 2.79 (t, J = 4.4 Hz,
1 H), 2.56–2.58 (dd, J = 4.4, 2.6 Hz, 1 H), 2.43 (s, 3 H).
Anal. Calcd for C11H14O3: C, 68.02; H, 7.27. Found: C, 67.92; H,
7.32.
2-{[4-(tert-Butyldimethylsiloxy)phenoxy]methyl}oxirane (15)
2-[(4-Hydroxyphenoxy)methyl]oxirane (6)
Prepared by the literature method22p as a colorless liquid.
Prepared by the literature method22h as a solid; mp 69 °C.
IR (neat): 2890, 1359, 1189 cm–1.
IR (neat): 3448 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.81–6.73 (m, 4 H), 4.14 (dd,
J = 10.9, 3.2 Hz, 1 H), 3.90 (dd, J = 10.9, 5.5 Hz, 1 H), 3.32 (m, 1
H), 2.89 (t, J = 4.5 Hz, 1 H), 2.74 (dd, J = 4.8, 2.6 Hz, 1 H), 0.97 (s,
9 H), 0.17 (s, 6 H).
13C NMR (100 MHz, CDCl3): d = 153.0, 149.8, 120.6, 115.5, 69.3,
50.2, 44.7, 25.7, 18.1, –4.4.
1H NMR (400 MHz, CDCl3): d = 6.86–6.74 (m, 4 H), 4.54 (s, OH),
4.16 (dd, J = 11.0, 3.2 Hz, 1 H), 3.90 (dd, J = 11.0, 4.0 Hz, 1 H),
3.33 (m, 1 H), 2.89 (t, J = 4.6 Hz, 1 H), 2.74 (dd, J = 4.92, 2.7 Hz,
1 H).
13C NMR (100 MHz, CDCl3): d = 152.3, 149.9, 115.9, 115.7, 69.3,
50.3, 44.6.
Anal. Calcd for C15H24O3Si: C, 64.24; H, 8.63. Found: C, 64.34; H,
8.53.
Anal. Calcd for C9H10O3: C, 65.05; H, 6.07. Found: C, 64.91; H,
6.11.
HRMS: m/z [M + Na] calcd for C15H24NaO3Si: 303.1392; found:
303.1396.
2-{[4-(Hydroxymethyl)phenoxy]methyl}oxirane (7)
Prepared by the literature method22j as a colorless liquid.
MoO2Cl2-Catalyzed Transformation of Epoxides to b-Alkoxy
Alcohols; General Procedure A
IR (neat): 3400, 1515 cm–1.
A mixture of epoxide (3 mmol), ROH (5 mL), and MoO2Cl2 (0.010
g, 5 mol%) was stirred under N2 at r.t. or 50 °C and monitored by
TLC. On completion, ROH was evaporated and the crude mixture
subjected to chromatography (silica gel, 100–200 mesh, EtOAc–
hexane mixtures) to give the pure b-alkoxy alcohols.
1H NMR (400 MHz, CDCl3): d = 7.28 (d, J = 8.5 Hz, 2 H), 6.90 (d,
J = 8.5 Hz, 2 H), 4.61 (d, J = 5.2 Hz, 2 H), 4.22 (dd, J = 11.0, 3.1
Hz, 1 H), 3.95 (dd, J = 11.0, 5.6 Hz, 1 H), 3.35 (m, 1 H), 2.90 (t,
J = 4.5 Hz, 1 H), 2.75 (dd, J = 4.84, 2.6 Hz, 1 H), 1.69 (t, J = 5.36
Hz, OH).
13C NMR (100 MHz, CDCl3): d = 158.0, 133.7, 128.6, 114.7, 68.7,
MoO2Cl2-Catalyzed Transformation of Epoxides to Acetonides;
General Procedure B
A mixture of epoxide (3 mmol), ketone (5 mL), and MoO2Cl2
(0.010 g, 5 mol%) was stirred under N2 at r.t. or 50 °C and moni-
tored by TLC. On completion, the ketone was evaporated and the
crude mixture was subjected to chromatography (basic alumina,
70–260 mesh, EtOAc–hexane mixtures) to give the pure acetonides.
64.9, 50.1, 44.6.
HRMS: m/z [M + Na]+ calcd for C10H12NaO3: 203.0684; found:
203.681.
Anal. Calcd for C10H12O3: C, 66.65; H, 6.71. Found: C, 66.45; H,
6.78.
2-[(4-Formylphenoxy)methyl]oxirane (8)
MoO2Cl2-Catalyzed Transformation of Epoxides to a-Alkoxy
Ketones; General Procedure C
Prepared by the literature method22l as a colorless solid.
IR (neat): 1689 cm–1.
A mixture of epoxide (1 mmol), ROH (3 mL), Oxone (1.2 equiv),
and MoO2Cl2 (0.030 g, 15 mol%) was stirred at r.t. or under reflux
conditions under air and monitored by TLC. On completion, ROH
was evaporated and the crude mixture was subjected to chromatog-
raphy (silica gel, 100–200 mesh, EtOAc–hexane mixtures) to give
the pure a-alkoxy ketones.
1H NMR (400 MHz, CDCl3): d = 9.88 (s, CHO), 7.85 (d, J = 8.6 Hz,
2 H), 7.03 (d, J = 8.6 Hz, 2 H), 4.35 (dd, J = 11.0, 2.84 Hz, 1 H),
4.02 (dd, J = 11.0, 5.9 Hz, 1 H), 3.38 (m, 1 H), 2.94 (t, J = 4.8 Hz,
1 H), 2.78 (dd, J = 4.8, 2.6 Hz, 1 H).
2-({4-[(Hydroxyimino)methyl]phenoxy}methyl)oxirane (9)
Epoxide 8 (1.78 g, 10 mmol) was stirred with hydroxylamine hy-
drochloride (1.40 g, 20 mmol) in MeOH (25 mL) at r.t. for 5 h. The
solid product was obtained in quantitative yield; mp 115 °C.
IR (neat): 2982, 1112 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.09 (s, 1 H), 7.50 (d, J = 8.6 Hz,
2 H), 6.92 (d, J = 8.6 Hz, 2 H), 4.25 (dd, J = 11.0, 2.9 Hz, 1 H), 3.97
2-Methoxy-2-phenylethanol (2a)
Following general procedure A using MeOH at r.t. gave 2a22a as a
colorless oil.
IR (neat): 3421 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.26–7.41 (m, 5 H), 4.32 (dd,
J = 4.0, 8.3 Hz, 1 H), 3.58–3.72 (m, 2 H), 3.31 (s, 3 H), 2.37 (s, OH).
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

PAPER
Ring-Opening Reactions of Epoxides
815
2-Ethoxy-2-phenylethanol (2b)
1-Methoxy-3-phenoxypropan-2-ol (18)
Following general procedure A using EtOH at r.t. gave 2b22a as a
colorless liquid.
Following general procedure A using MeOH at 50 °C gave 1822a as
a colorless liquid.
IR (neat): 3425 cm–1.
IR (neat): 3424 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.27–7.39 (m, 5 H), 4.42 (dd,
J = 4.2, 8.2 Hz, 1 H), 3.56–3.70 (m, 2 H), 3.36–3.53 (m, 2 H), 2.35
(br, OH), 1.22 (t, J = 7.0 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.30–6.89 (m, 5 H), 4.12–4.18 (m,
1 H), 3.99–4.01 (m, 2 H), 3.50–3.59 (m, 2 H), 3.39 (s, 3 H), 3.00 (br,
OH).
2-Isopropoxy-2-phenylethanol (2c)
Following general procedure A using i-PrOH at r.t. gave 2c22a as a
colorless liquid.
1-(4-Hydroxyphenoxy)-3-methoxypropan-2-ol (19)
Following general procedure A using MeOH at 50 °C gave 19 as a
white solid; mp 85 °C.
IR (neat): 3428 cm–1.
IR (neat): 3450, 3429 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.26–7.37 (m, 5 H), 4.53 (dd,
J = 4.6, 7.9 Hz, 1 H), 3.54–3.64 (m, 3 H), 2.55 (br, OH), 1.19 (d,
J = 5.9 Hz, 3 H), 1.13 (d, J = 6.2 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 6.80–6.73 (m, 4 H), 4.95 (s, OH),
4.14 (m, 1 H), 3.94 (m, 2 H), 3.55 (m, 2 H), 3.41 (s, 3 H), 2.62 (d,
OH).
13C NMR (100 MHz, CDCl3): d = 152.7, 149.9, 116.0, 115.7, 73.4,
2-tert-Butoxy-2-phenylethanol (2d)
69.7, 69.1, 59.2.
Following general procedure A using t-BuOH at r.t. gave 2d22a as a
white solid; mp 73–76 °C.
HRMS: m/z [M + H] calcd for C10H15O4: 199.0970; found:
199.0966.
IR (neat): 3449 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.23–7.36 (m, 5 H), 4.62 (dd,
J = 4.4, 8.2 Hz, 1 H), 3.43–3.57 (m, 2 H), 2.27 (br, OH), 1.17 (s, 9
Anal. Calcd for C10H14O4: C, 60.59; H, 7.12. Found: C, 60.67; H,
7.06.
H).
1-[4-(Hydroxymethyl)phenoxy]-3-methoxypropan-2-ol (20)
Following general procedure A using MeOH at 50 °C gave 20 as a
colorless liquid.
IR (neat): 3412, 3380 cm–1.
2-Acetoxy-2-phenylethanol (2e)
Following general procedure A using AcOH at r.t. gave 2e22b as a
colorless oil.
1H NMR (400 MHz, CDCl3): d = 7.26 (d, J = 8.5 Hz, 2 H), 6.87 (d,
J = 8.5 Hz, 2 H), 4.58 (s, 2 H), 4.14 (m, 1 H), 3.98 (m, 2 H), 3.55
(m, 2 H), 3.40 (s, 3 H), 2.82 (d, OH), 2.11 (s, OH).
13C NMR (100 MHz, CDCl3): d = 158.2, 133.7, 128.6, 114.6, 73.5,
69.1, 69.05, 64.8, 59.2.
IR (neat): 3472, 1730 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.33 (m, 5 H), 5.83 (dd, J = 7.1,
4.6 Hz, 1 H), 3.88–3.71 (m, 2 H), 3.24 (br, OH), 2.12 (s, 3 H).
2-Phenylethanol (2f)
Following general procedure A using H2O at r.t. gave 2f22c as color-
less needles; mp 64–65 °C.
HRMS: m/z [M + Na] calcd C11H16NaO4: 235.0946; found:
235.0944.
IR (neat): 3500 cm–1.
Anal. Calcd for C11H16O4: C, 62.25; H, 7.60. Found: C, 61.98; H,
7.32.
1H NMR (400 MHz, CDCl3): d = 7.31 (m, 5 H), 4.78 (dd, J = 8.1,
3.6 Hz, 1 H), 3.75 (dd, J = 11.3, 3.6 Hz, 1 H), 3.66 (dd, J = 11.3, 8.1
Hz, 1 H), 3.03 (br s, OH), 2.61 (br s, OH).
1-(4-Formylphenoxy)-3-methoxypropan-2-ol (21)
Following general procedure A using MeOH at 50 °C gave 21 as a
colorless liquid.
IR (neat): 3410, 1686 cm–1.
1H NMR (400 MHz, CDCl3): d = 9.88 (s, CHO), 7.83 (d, J = 8.6 Hz,
2 H), 7.03 (d, J = 8.6 Hz, 2 H), 4.20–4.09 (m, 3 H), 3.58 (m, 2 H),
3.42 (s, 3 H), 2.70 (s, OH).
2-Methoxycyclohexanol (16)
Following general procedure A using MeOH at r.t. gave 1622a as a
colorless liquid.
IR (neat): 3440 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.44–3.3.3.41 (m, 1 H), 3.40 (s, 3
H), 2.98–2.90 (m, 1 H), 2.57 (br s, OH), 2.15–1.99 (m, 2 H), 1.76–
1.69 (m, 2 H), 1.31–1.06 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 190.8, 163.5, 132.0, 130.2, 114.8,
73.2, 69.2, 68.8, 59.3.
HRMS: m/z [M + Na] calcd for C11H14NaO4: 233.0790; found:
233.0787.
1-(3,4-Dimethoxyphenyl)-3-methoxypropan-2-ol (17)
Following general procedure A using MeOH at 50 °C gave 1722r as
a colorless liquid.
IR (neat): 3422, 1152 cm–1.
Anal. Calcd for C11H14O4: C, 62.85; H, 6.71. Found: C, 62.95; H,
6.59.
1H NMR (400 MHz, CDCl3): d = 6.82–6.75 (m, 3 H), 4.00 (m, 1 H),
3.87 (s, 3 H), 3.86 (s, 3 H), 3.40 (dd, J = 3.4, 9.5 Hz, 1 H), 3.39 (s,
3 H), 3.30 (dd, J = 9.4, 7.0 Hz, 1 H), 2.73 (d, J = 6.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 148.9, 147.7, 130.4, 121.2, 112.5,
111.5, 76.0, 71.3, 59.0, 55.9, 55.8, 39.4.
1-{4-[(Hydroxyimino)methyl]phenoxy}-3-methoxypropan-2-ol
(22)
Following general procedure A using MeOH at 50 °C gave 22 as a
solid; mp 78 °C.
IR (neat): 3491, 1110 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.97 (s, 1 H), 7.35 (d, J = 8.5 Hz,
2 H), 6.77 (d, J = 8.5 Hz, 2 H), 4.10 (m, 1 H), 3.93 (m, 2 H), 3.50
(m, 2 H), 3.32 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 159.9, 149.69, 128.5, 125.0,
114.8, 73.7, 69.0, 68.8, 59.2.
HRMS: m/z [M + Na] calcd for C12H18NaO4: 249.1103; found.
249.1109.
Anal. Calcd for C12H18O4: C, 63.70; H, 8.02. Found: C, 63.59; H,
7.99.
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

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K. Jeyakumar, D. K. Chand
PAPER
HRMS: m/z [M + H] calcd for C11H16NO4: 226.1079; found:
226.1077.
1H NMR (400 MHz, CDCl3): d = 6.79–6.73 (m, 4 H), 4.13 (m, 1 H),
3.95 (m, 2 H), 3.57 (m, 2 H), 3.40 (s, 3 H), 2.65 (br, OH), 0.97 (s, 9
H), 0.16 (s, 6 H).
13C NMR (100 MHz, CDCl3): d = 153.0, 149.7, 120.6, 115.3, 73.5,
69.5, 69.1, 59.2, 25.7, 18.1, –4.4.
Anal. Calcd for C11H15NO4: C, 58.66; H, 6.71; N, 6.22. Found: C,
58.57; H, 6.33; N, 6.18.
1-(Allyloxy)-3-methoxypropan-2-ol (23)
Following general procedure A using MeOH at r.t. gave 2322a as a
colorless liquid.
IR (neat): 3403, 1195 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.91 (m, 1 H), 5.30–5.18 (m, 2 H),
4.03–3.99 (m, 3 H), 3.41–3.55 (m, 4 H), 3.39 (s, 3 H), 2.61 (d, J = 4
Hz, OH).
HRMS: m/z [M + Na] calcd for C16H28NaO4Si: 335.1655; found:
335.1648.
Anal. Calcd for C16H28O4Si: C, 61.50; H, 9.03. Found: C, 61.42; H,
9.15.
2,2-Dimethyl-4-phenyl-1,3-dioxolane (29)
Following general procedure B using acetone at r.t. gave 297f as a
colorless oil.
1-Methoxy-3-(prop-2-ynyloxy)propan-2-ol (24)
Following general procedure A using MeOH at r.t. gave 24 as a col-
orless liquid.
IR (neat): 3423, 1450 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.20 (d, J = 2.4 Hz, 2 H), 3.99 (m,
1 H), 3.63–3.41 (m, 4 H), 3.39 (s, 3 H), 2.45 (t, J = 2.2 Hz, 1 H).
IR (neat): 3036, 1230 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.25 (m, 5 H), 5.00 (dd, J = 6.2, 8
Hz, 1 H), 4.23 (dd, J = 6.6, 8 Hz, 1 H), 3.62 (dd, J = 8.2, 16 Hz, 1
H), 1.48 (s, 3 H), 1.40 (s, 3 H).
2,2-Diethyl-4-phenyl-1,3-dioxolane (30)
Following general procedure B using propan-3-one at r.t. gave 3022d
as a colorless oil.
IR (neat): 3036, 1230 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.30 (m, 5 H), 5.03 (dd, J = 6.1,
8.9 Hz, 1 H), 4.72 (dd, J = 6.1, 8.0 Hz, 1 H), 3.62 (dd, J = 6.1, 16
Hz, 1 H), 1.70–1.82 (m, 4 H), 0.99 (t, J = 7.5 Hz, 3 H), 0.95 (t,
J = 7.5 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 79.4, 74.8, 73.6, 71.0, 69.3, 59.2,
58.6.
HRMS: m/z [M + Na] calcd for C7H12NaO3: 167.0684; found:
167.0683.
Anal. Calcd for C7H12O3: C, 58.32; H, 8.39. Found: C, 58.02; H,
8.61.
1-(Benzyloxy)-3-methoxypropan-2-ol (25)
Following general procedure A using MeOH at 50 °C gave 2516a as
a colorless liquid.
IR (neat): 3429 3062 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.35–7.28 (m, 5 H), 4.56 (s, 2 H),
4.01–3.97 (m, 1 H), 3.59–3.41 (m, 4 H), 3.37 (s, 3 H), 2.67 (br, OH).
1,2-(Isopropylidenedioxy)cyclohexane (31)
Following general procedure B using acetone at r.t. gave 317f as a
colorless oil.
IR (neat): 2980, 1260 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.34–4.05 (m, 2 H), 2.58–2.07 (m,
4 H), 1.35 (s, 6 H), 1.24–1.00 (m, 4 H).
1-Methoxy-3-(tosyloxy)propan-2-ol (26)
Following general procedure A using MeOH at 50 °C gave 2622o as
a colorless liquid.
IR (neat): 3422, 2896, 1189 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.80 (d, J = 8.3 Hz, 2 H), 7.35 (d,
J = 8.3 Hz, 2 H), 4.01 (m, 3 H), 3.43 (m, 2 H), 3.33 (s, 3 H), 2.45 (s,
3 H), 2.36 (d, J = 5.4 Hz, OH).
4-(3,4-Dimethoxybenzyl)-2,2-dimethyl-1,3-dioxolane (32)
Following general procedure B using acetone at 50 °C gave 32 as a
colorless liquid.
IR (neat): 2985, 2360, 1259 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.81–6.73 (m, 3 H), 4.30 (q, 1 H),
3.96 (dd, J = 7.9, 6.0 Hz, 1 H), 3.87 (s, 3 H), 3.85 (s, 3 H), 3.63 (t,
J = 7.5 Hz, 1 H), 2.95 (dd, J = 13.7, 6.0 Hz, 1 H), 2.72 (dd, J = 13.7,
7.1 Hz, 1 H), 1.43 (s, 3 H), 1.35 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 145.0, 132.6, 129.3, 128.0, 72.4,
70.5, 68.2, 59.2, 21.6.
13C NMR (100 MHz, CDCl3): d = 148.8, 147.7, 130.0, 121.0, 112.4,
111.2, 109.1, 76.7, 68.9, 55.88, 55.83, 39.6, 27.0, 25.7.
HRMS: m/z [M + Na] calcd for C11H16NaO5S: 283.0616; found:
283.0617.
HRMS: m/z [M + Na] calcd for C14H20NaO4: 275.1259; found.
275.1252.
Anal. Calcd for C11H16O5S: C, 50.75; H, 6.20. Found: C, 51.05; H,
6.01.
Anal. Calcd for C14H20O4: C, 66.65; H, 7.99. Found: C, 66.35; H,
8.12.
1-Methoxyoctan-2-ol (27)
Following general procedure A using MeOH at 50 °C gave 277g as
a colorless liquid.
2,2-Dimethyl-4-(phenoxymethyl)-1,3-dioxolane (33)
Following general procedure B using acetone at 50 °C gave 337f as
a white solid; mp 68 °C.
IR (neat): 3450 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.00–3.65 (m, 1 H), 3.45 (s, 3 H),
3.38–3.25 (m, 2 H), 2.95 (br, OH), 1.52–1.12 (m, 10 H), 0.85 (t,
J = 6.0 Hz, 3 H).
IR (neat): 3070, 1240 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.47–6.72 (m, 5 H), 4.65–3.64 (m,
5 H), 1.42 (s, 3 H), 1.30 (s, 3 H).
1-[4-(tert-Butyldimethylsiloxy)phenyl]-3-methoxypropan-2-ol
(28)
Following general procedure A using MeOH at 50 °C gave 28 as a
colorless liquid.
4-[(4-Hydroxyphenoxy)methyl]-2,2-dimethyl-1,3-dioxolane
(34)
Following general procedure B using acetone at 50 °C gave 3422i as
a white solid; mp 68 °C.
IR (neat): 3450, 1240 cm–1.
IR (neat): 3469, 2936, 1299 cm–1.
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Ring-Opening Reactions of Epoxides
817
1H NMR (400 MHz, CDCl3): d = 6.80–6.73 (m, 4 H), 4.76 (s, OH),
4.45 (m, 1 H), 4.15 (dd, J = 8.3, 6.3 Hz, 1 H), 4.01 (dd, J = 9.5, 2.5
Hz, 1 H), 3.90–3.86 (m, 2 H), 1.46 (s, 3 H), 1.40 (s, 3 H).
4-[(Benzyloxy)methyl]-2,2-dimethyl-1,3-dioxolane (40)
Following general procedure B using acetone at 50 °C gave 4015f as
a colorless liquid.
IR (neat): 1240 cm–1.
4-{[4-(Hydroxymethyl)phenoxy]methyl}-2,2-dimethyl-1,3-di-
oxolane (35)
1H NMR (400 MHz, CDCl3): = 7.32 (m, 5 H), 4.57 (m, 2 H), 4.29
(m, 1 H), 4.05 (dd, J = 8.2, 6.2 Hz, 1 H), 3.73 (dd, J = 8.2, 6.5 Hz,
1 H), 3.55 (dd, J = 10.0, 5.6 Hz, 1 H), 3.46 (dd, J = 10, 5.6 Hz, 1 H),
1.42 (s, 3 H), 1.36 (s, 3 H).
Following general procedure B using acetone at 50 °C gave 3522k as
a white solid; mp 58 °C.
IR (neat): 3450, 1240 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.18 (d, J = 8.8 Hz, 2 H), 6.80 (d,
J = 8.8 Hz, 2 H), 4.77 (s, OH), 4.50 (s, 2 H), 4.37 (m, 1 H), 4.06 (dd,
J = 8.36, 6.36 Hz, 1 H), 3.95 (dd, J = 9.5, 2.5 Hz, 1 H), 3.84–3.74
(m, 2 H), 1.37 (s, 3 H), 1.31 (s, 3 H).
2,2-Dimethyl-4-[(tosyloxy)methyl]-1,3-dioxolane (41)
Following general procedure B using acetone at 50 °C gave 4122s as
a colorless liquid.
IR (neat): 2896, 1259, 1189 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.79 (d, J = 8.0 Hz, 2 H), 7.35 (d,
J = 8.0 Hz, 2 H), 4.27 (m, 1 H), 4.0 (m, 3 H), 3.76 (m, 1 H), 2.45 (s,
3 H), 1.34 (s, 3 H), 1.31 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 145.0, 132.6, 129.9, 128.0, 110.0,
72.9, 69.4, 66.1, 26.6, 25.1, 21.6.
4-[(4-Formylphenoxy)methyl]-2,2-dimethyl-1,3-dioxolane (36)
Following general procedure B using acetone at 50 °C gave 36 as a
colorless liquid.
IR (neat): 2986, 1689 cm–1.
1H NMR (400 MHz, CDCl3): d = 9.89 (s, CHO), 7.84 (d, J = 8.8 Hz,
2 H), 7.02 (d, J = 8.8 Hz, 2 H), 4.50 (q, 1 H), 4.19 (dd, J = 8.4, 6.3
Hz, 1 H), 4.13 (dd, J = 9.5, 5.4 Hz, 1 H), 4.03 (dd, J = 9.6, 5.6 Hz,
1 H), 3.92 (dd, J = 8.6, 5.6 Hz, 1 H), 1.46 (s, 3 H), 1.41 (s, 3 H).
Anal. Calcd for C13H18O5S: C, 54.53; H, 6.34. Found: C, 54.33; H,
6.25.
HRMS: m/z [M + Na] calcd for C13H18NaO5S: 309.0773; found:
13C NMR (100 MHz, CDCl3): d = 190.7, 163.4, 131.9, 130.2, 114.8,
109.9, 73.7, 68.9, 66.6, 26.7, 25.3.
309.0776.
4-Hexyl-2,2-dimethyl-1,3-dioxolane (42)
Following general procedure B using acetone at 50 °C gave 427f as
a colorless liquid.
HRMS: m/z [M + H] calcd for C13H17O4: 237.1127; found:
237.1122.
Anal. Calcd for C13H16O4: C, 66.09; H, 6.83. found: 66.19; H, 6.88.
IR (neat): 2970, 1250 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.20–3.31 (m, 3 H), 1.72–1.13 (m,
16 H), 0.82 (t, J = 7 Hz, 3 H).
4-({4-[(Hydroxyimino)methyl]phenoxy}methyl)-2,2-dimethyl-
1,3-dioxolane (37)
Following general procedure B using acetone at 50 °C gave 37 as a
solid; mp 95 °C.
IR (neat): 1259, 1089 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.08 (s, 1 H), 7.80 (s, =NOH),
7.50 (d, J = 8.3 Hz, 2 H), 6.91 (d, J = 8.3 Hz, 2 H), 4.49 (q, 1 H),
4.17 (t, J = 7.0 Hz, 1 H), 4.07 (dd, J = 9.3, 5.5 Hz, 1 H), 3.99–3.89
(m, 2 H), 1.47 (s, 3 H), 1.41 (s, 3 H).
4-{4-(tert-Butyldimethylsiloxy)phenoxy]methyl}-2,2-dimethyl-
1,3-dioxolane (43)
Following general procedure B using acetone at 50 °C gave 43 as a
colorless liquid.
IR (neat): 2890, 1320 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.79–6.73 (m, 4 H), 4.44 (q, 1 H),
4.15 (dd, J = 8.3, 6.4 Hz, 1 H), 4.00 (dd, J = 9.4, 5.4 Hz, 1 H), 3.88
(m, 2 H), 1.45 (s, 3 H), 1.39 (s, 3 H), 0.97 (s, 9 H), 0.15 (s, 6 H).
13C NMR (100 MHz, CDCl3): d = 153.1, 149.8, 120.6, 115.4,
109.6, 74.1, 69.4, 66.9, 26.8, 25.7, 25.4, 18.2, –4.4.
13C NMR (100 MHz, CDCl3): d = 160.0, 149.8, 128.4, 125.1, 114.8,
109.8, 73.9, 68.8, 66.8, 26.7, 25.3.
HRMS: m/z [M + H] calcd for C13H18NO4: 252.1236; found:
252.1239.
HRMS: m/z [M + Na] calcd for C18H30NaO4Si: 361.1811; found
361.1812.
Anal. Calcd for C13H17NO4: C, 62.14; H, 6.82; N, 5.57. Found: C,
61.84; H, 6.89; N, 5.86.
Anal. Calcd for C18H30O4Si: C, 63.87; H, 8.93. Found: C, 63.76; H,
8.97.
4-[(Allyloxy)methyl]-2,2-dimethyl-1,3-dioxolane (38)
Following general procedure B using acetone at r.t. gave 387f as a
colorless liquid.
IR (neat): 1195 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.91 (m, 1 H), 5.30–5.18 (m, 2 H),
4.28 (m, 1 H), 4.02–4.08 (m, 3 H), 3.74 (dd, J = 8.36, 6.36 Hz, 1 H),
3.51 (dd, J = 9.6, 5.6 Hz, 1 H), 3.46 (dd, J = 8.6, 5.6 Hz, 1 H), 1.46
(s, 3 H), 1.41 (s, 3 H).
Methyl 2-Methoxy-2-phenylacetate (45)
Following general procedure C using MeOH and Oxone (2 equiv)
at reflux gave 4522e as a colorless oil.
IR (neat): 1758 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.34 (s, 5 H), 4.70 (s, 1 H), 3.62
(s, 3 H), 3.32 (s, 3 H).
2-Methoxycyclohexanone (44a)
2,2-Dimethyl-4-[(prop-2-ynyloxy)methyl]-1,3-dioxolane (39)
Following general procedure B using acetone at r.t. gave 3922m as a
colorless liquid.
IR (neat): 1450 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.27–4.31 (m, 1 H), 4.21–4.22 (m,
2 H), 4.06 (dd, J = 8.2, 6.4 Hz, 1 H), 3.72–3.75 (m, 1 H), 3.56–3.63
(m, 2 H), 2.45–2.48 (t, J = 2.2 Hz, 1 H), 1.43 (s, 3 H), 1.36 (s, 3 H).
Following general procedure C using MeOH at reflux gave 44a22f
as a colorless liquid.
IR (neat): 1720 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.67 (m, 1 H), 3.36 (s, 3 H), 2.45
(m, 1 H), 2.21 (m, 2 H), 1.89 (m, 2 H), 1.64 (m, 3 H).
Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

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K. Jeyakumar, D. K. Chand
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2-Ethoxycyclohexanone (44b)
Anal. Calcd for C7H12O3: C, 58.32; H, 8.39. Found: C, 58.23; H,
8.24.
Following general procedure C using EtOH at reflux gave 44b22f as
a colorless liquid.
1-Methoxy-3-(prop-2-ynyloxy)propan-2-one (50)
Following general procedure C using MeOH at reflux gave 50 as a
colorless liquid.
IR (neat): 1730, 1453 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.33 (s, 2 H), 4.27 (d, J = 2.4 Hz,
2 H), 4.19 (s, 2 H), 3.43 (s, 3 H), 2.50 (t, J = 2.3 Hz, 1 H).
IR (neat): 1720 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.78 (m, 1 H), 3.64 (m, 1 H), 3.40
(m, 1 H), 2.26 (m, 1 H), 2.18 (m, 1 H), 1.90 (m, 2 H), 1.75 (m, 2 H),
1.70 (m, 2 H), 1.20 (t, J = 7.0 Hz, 3 H).
2-Isopropoxycyclohexanone (44c)
Following general procedure C using i-PrOH at reflux gave 44c22f
as a colorless liquid.
13C NMR (100 MHz, CDCl3): d = 205.1, 78.5, 76.2, 75.7, 72.8,
59.5, 58.5.
IR (neat): 1720 cm–1.
Anal. Calcd for C7H10O3: C, 59.14; H, 7.09. Found: C, 58.91; H,
6.91.
1H NMR (400 MHz, CDCl3): d = 3.84 (m, 1 H), 3.60 (sept, J = 7.0
Hz, 1 H), 1.50– 2.70 (m, 8 H), 1.15 (d, J = 7.0 Hz, 3 H), 1.08 (d,
J = 7.0 Hz, 3 H).
HRMS: m/z [M + Na] calcd for C7H10NaO3: 165.0528; found:
165.0532.
1-(3,4-Dimethoxyphenyl)-3-methoxypropan-2-one (46)
Following general procedure C using MeOH at reflux gave 46 as a
colorless liquid.
IR (neat): 2937, 1723 cm–1.
1H NMR (400 MHz, CDCl3): d = 6.74–6.83 (m, 3 H), 4.06 (s, 2 H),
3.87 (s, 6 H), 3.69 (s, 2 H), 3.39 (s, 3 H).
1-(Benzyloxy)-3-methoxypropan-2-one (51)
Following general procedure C using MeOH at reflux gave 5116a as
a colorless liquid.
IR (neat): 1730 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.38–7.29 (m, 5 H), 4.59 (s, 2 H),
4.22 (s, 2 H), 4.21 (s, 2 H), 3.40 (s, 3 H).
13C NMR (100 MHz, CDCl3): d = 206.1, 149.0, 148.1, 125.7, 121.6,
112.3, 111.3, 76.7, 59.2, 55.8 (2 C), 45.7.
1-Methoxy-3-(tosyloxy)propan-2-one (52)
Following general procedure C using MeOH at reflux gave 5222o as
a colorless liquid.
IR (neat): 1732 cm–1.
1H NMR (400 MHz, CDCl3): d = 8.84 (d, J = 8.2 Hz, 2 H), 7.35 (d,
J = 8.2 Hz, 2 H), 4.76 (s, 2 H), 4.16 (s, 2 H), 3.41 (s, 3 H), 2.47 (s,
3 H).
HRMS: m/z [M + Na] calcd for C12H16NaO4: 247.0946; found:
247.0946.
Anal. Calcd for C12H16O4: C, 64.27; H, 7.19. Found: C, 64.45; H,
6.98.
1-Methoxy-3-phenoxypropan-2-one (47)
Following general procedure C using MeOH at reflux gave 47.22g
1-Methoxyoctan-2-one (53)
Following general procedure C using MeOH at reflux gave 53 as a
colorless liquid.
IR (neat): 1736 cm–1.
IR (neat): 1735 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.33 (s, 3 H), 4.20 (s, 2 H), 4.65
(s, 2 H), 6.8–7.5 (m, 5 H).
1-(4-Formylphenyl)-3-methoxypropan-2-one (48)
Following general procedure C using MeOH at r.t. gave 48 as a col-
orless liquid.
IR (neat): 1723, 1689 cm–1.
1H NMR (400 MHz, CDCl3): d = 4.0 (s, 2 H), 3.42 (s, 3 H), 2.42 (t,
J = 7.4 Hz, 2 H), 1.27–1.68 (m, 8 H), 0.87 (t, J = 6.3 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 208.9, 77.7, 59.4, 38.9, 31.7, 29.0,
23.4, 22.6, 14.1.
1H NMR (400 MHz, CDCl3): d = 9.90 (s, CHO), 7.85 (d, J = 8.6 Hz,
2 H), 7.00 (d, J = 8.6 Hz, 2 H), 4.89 (s, 2 H), 4.29 (s, 2 H), 3.50 (s,
3 H).
13C NMR (100 MHz, CDCl3): d = 202.8, 190.7, 162.4, 132.0, 130.7,
114.8, 76.3, 71.2, 59.6.
Anal. Calcd for C9H18O2: C, 68.31; H, 11.47. Found: C, 68.01; H,
11.52.
HRMS: m/z [M + Na] calcd for C9H18NaO2: 159.1385; found:
159.1381.
Anal. Calcd for C11H12O4: C, 63.45; H, 5.81. Found: C, 63.58; H,
5.90.
Acknowledgment
This study was supported by a grant in aid for scientific research
from the CSIR, (No. 01(2108)/07/EMR-II New Delhi, India.). K.J.
thanks CSIR, New Delhi for a Senior Research Fellowship.
HRMS: m/z [M + H] calcd for C11H13O4: 209.0808; found:
209.0814.
1-(Allyloxy)-3-methoxypropan-2-one (49)
Following general procedure C using MeOH at reflux gave 49 as a
colorless liquid.
References
IR (neat): 1732 cm–1.
1H NMR (400 MHz, CDCl3): d = 5.91 (m, 1 H), 5.28 (m, 2 H), 4.21
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13C NMR (100 MHz, CDCl3): d = 205.8, 133.6, 118.2, 76.25, 73.6,
72.5, 59.4.
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Synthesis 2008, No. 5, 807–819 © Thieme Stuttgart · New York

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