Triflic acid catalyzed oxidative lactonization and diacetoxylation of alkenes using peroxyacids as oxidants

Article abstract of DOI:10.1021/jo202491y

A clean and efficient diacetoxylation reaction of alkenes catalyzed by triflic acid using commercially available peroxyacids as the oxidants has been developed. This method was also applied in oxidative lactonizations of unsaturated carboxylic acids in good to high yields.

Full text of DOI:10.1021/jo202491y

Note
pubs.acs.org/joc
Triflic Acid Catalyzed Oxidative Lactonization and Diacetoxylation of
Alkenes Using Peroxyacids as Oxidants
Yan-Biao Kang† and Lutz H. Gade*,†,‡
†Catalysis Research Laboratory (CaRLa), Im Neuenheimer Feld 584, 69120 Heidelberg, Germany
‡Anorganisch-Chemisches Institut, Universitat Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
̈
S
* Supporting Information
ABSTRACT: A clean and efficient diacetoxylation reaction of alkenes catalyzed by triflic
acid using commercially available peroxyacids as the oxidants has been developed. This
method was also applied in oxidative lactonizations of unsaturated carboxylic acids in good
to high yields.
he dihydroxylation of alkenes is an important reaction in
organic synthesis. Generally, there are three basic
Scheme 1. Diacetoxylation of Alkenes Mediated by in Situ
Generated Catalytic Amount of Hypervalent Iodine Reagent
T
methods for the construction of 1,2-glycols: the one-step
Upjohn syn-dihydroxylation1 together with its asymmetric
version developed by Sharpless,2 the two-step reaction reported
by Prev
́
ost and Woodward,3,4 as well as the ring-opening
dihydroxylation of epoxides.5−7 The one-step processes are in
principle the most efficient, but the use of highly toxic and
expensive osmium tetroxide represents a serious drawback.
Recently, we reported a metal free diacetoxylation of alkenes
catalyzed by triflic acid using hypervalent iodine in the form of
PhI(OAc)2 as oxidant.8 This reaction was previously described
as metal catalyzed, involving high-valent PdIV and CuIII
intermediates;9 however, a detailed mechanistic study has
drawn the earlier interpretation into question.8,9 Another recent
report concerned the Pd(OAc)2-catalyzed diacetoxylation of
alkenes using peracetic acid as oxidant in the presence of acetic
anhydride.10 During the preparation of this manuscript, Afonso
et al. described a p-toluenesulfonic acid (20−100 mol %)
catalyzed dihydroxylation of alkenes using H2O2 in aqueous
media at 50 °C.11 In conclusion, the efficient dihydroxylation of
alkenes with nontoxic and cheap catalysts remains a challenge.
In our previous triflic acid catalyzed diacetoxylation reaction
using (diacetoxyiodo)benzene as oxidant, we found that the
reaction of aliphatic alkenes normally requires elevated
temperature and longer reaction times compared to arylated
derivatives.8 The use of the relatively expensive hypervalent
iodine reagent, along with the production of iodobenzene as a
waste, limits the scope of this synthetic method. The oxidant
(diacetoxyiodo)benzene is prepared by the treatment of
iodobenzene with peracetic acid in acetic acid,12 and thus we
aimed to develop a strategy using in situ generated catalytic
amounts of (diacetoxyiodo)benzene in the presence of
peroxyacids as co-oxidants. As shown in Scheme 1, our initial
test started with the diacetoxylation of 1-octene in the presence
of 10 mol % (diacetoxyiodo)benzene [PhI(OAc)2] in the
presence of 20 mol % triflic acid (TfOH) using 2 equiv of
peracetic acid. The regeneration of hypervalent iodanes was
supposed to be achieved readily with AcO2H. In fact, the
reactions with or without PhI(OAc)2 gave very similar results
(methods A and B); however, not unexpectedly, the reaction in
the absence of TfOH gave 1,2-epoxyoctane as major product
(method C). These findings suggested that the peroxyacid itself
probably played the essential role in this reaction with TfOH
acting as a catalyst or promoter.
Next, a variety of Lewis acids were investigated to identify
the optimal catalytic system. As shown in Table 1, the reaction
in the presence of 10 mol % of TfOH, in 20 h and at ambient
temperature, gave 84% conversion, including 20% monoacetox-
ylation products (MAOs) and 64% 1,2-diacetoxyoctane (DAO)
(entry 1). Sn(OTf)2 and TMSOTf gave similar results with
DAO as major product (entries 4 and 6), while the background
reaction mainly furnished the epoxide (entry 5). TfOH was
Received: December 5, 2011
Published: January 9, 2012
© 2012 American Chemical Society
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Note
a
Table 1. Catalysts Screening for Peracetic Acid Dioxygenation of 1-Octene
entry
1
catalyst
TfOH
conv (%)
2a (%)
3a + 4a (%)
5a (%)
84
89
0
0
20
25
82 (0)
13
4
64
b
2
TfOH
64
c
3
TfOH
100
74
0
18 (99)
4
Sn(OTf)2
0
47
0
d
5
78
70
0
6
TMSOTf
70
19
38
33
37
45
19
34
25
29
35
0
7
Ca(OTf)2
Ba(OTf)2
Mg(OTf)2
Zn(OTf)2
AgN(Tf)2
Cu(OTf)2
Pd(OAc)2
Pd(OTf)2(Ln)
70
16
25
3
8
68
0
9
62
0
10
11
12
69
0
7
67
30
0
0
66
12
0
e
13
e,f
99
48
0
14
100
12
a
2.0 equiv of AcO2H, 10 mol % of catalyst, room temperature (water bath), 20 h. The conversions and the ratios of the reaction mixtures were
b
c
1
estimated on the basis of H NMR using 1,2-dimethoxylethane as internal standard. 3-Chloroperoxybenzoic acid instead of AcO2H. Hydrogen
peroxide (30%) instead of AcO2H; the numbers in parentheses are the conversions after the treatment with Ac2O. Average of three runs for the
unstable reaction. Complex products, including the isomers of octenes, octadienes, and their corresponding oxidation products, Wacker−Tsuji-type
oxidation products (ketones, 1- and 3-acetoxyloctenes), were seen on GC−MS. Pd(H2 O)2(OTf)2(R-BINAP) was used.
d
e
f
Scheme 2. Inhibiting Effect of Base on the Background
Epoxidation Reaction
of TfOH (Figure 1D), only very slow conversion was observed
in the back-ground reaction of ring-opening of 1,2-epoxyoctane
(Figure 1C).
All reactions were run in acetic acid as reaction medium,
which proved to be essential for the initial peroxyacid
epoxidation step. The presence of 10 mol % of Proton Sponge
totally inhibited the conversion of styrene to epoxide and its
further transformations (Scheme 2).
On the basis of the aforementioned findings, an efficient
metal-free diacetoxylation of alkenes catalyzed by TfOH using
peroxyacids as oxidant was developed (Table 2). Under these
conditions, both linear and cyclic aliphatic alkenes were
converted to diacetoxylation products in good to excellent
isolated yields: Terminal alkenes (entries 1−3) and cyclic
alkenes (entries 6−7) gave the corresponding diacetoxylation
products also in high yields. On the other hand, the extension
of the carbon chain of a terminal alkene led to a decrease in
yield (entry 4), as also found for aromatic alkenes such as
styrenes (entries 8−9). Both trans- and cis-stilbenes gave syn-
diacetoxylation products with low diastereoselectivities (entries
10−11). The two-step reaction using m-CPBA as oxidant
generally afforded diacetoxylation products in higher yields
(yields in parentheses in entries 1, 2, 4, and 8). Normally, the
reactions using m-CPBA are clean, but the generation of 3-
chlorobenzoic acid and its acetyl anhydride may give rise to
difficulties in the purification of the reaction products on silica
gel columns which is why the use of peracetic acid generally
appears to be preferable.
found to have no dramatic accelerating effect in the epoxidation
step but greatly enhanced the subsequent ring-opening
acetoxylation of the epoxide, to the extent that no epoxide
intermediate was observed under these conditions. The triflates
of alkali earth metals and zinc(II) afforded moderate
conversions of MAOs as major products (entries 7−10).
Copper(II) triflate gave 12% of DAO and 34% MAOs (entry
12), whereas in Pd(OAc)2 catalysis,10 the conversion of 1-
octene was very rapid, with only epoxide and MAOs being
primarily formed (entry 13). Finally, the triflatopalladium(II)
catalyst gave 12% DAO together with 29% MAOs (entry 14),
along with a complex mixture of side products which were
detected by GC−MS.
To further explore the catalytic and noncatalytic oxidation of
1-octene, in situ 1H NMR studies were carried out. In Figure 1
the conversion−time plots clearly show the components of
reaction mixtures. The mixture of MAOs and DAO was formed
at an early stage of the TfOH catalyzed reaction (Figure 1B)
while no epoxide was detected. During the course of the
reaction, MAOs continuously converted to DAO, giving rise to
the high final yield of DAO. The absence of epoxide in TfOH
catalysis suggests extremely fast ring-opening-acetylation of the
epoxide intermediate, as also found by Afonso and co-workers
for the TosOH-catalyzed dihydroxylation.11 To prove this, 1,2-
epoxyoctane was subjected to a variety of reaction conditions in
the presence or absence of TfOH: Whereas the epoxide
disappeared prior to the first NMR experiment in the presence
The peroxyacid based method is also very efficient in the
oxidative lactonization of ω-unsaturated carboxylic acids to
afford five-membered lactones (entries 1−3, Table 3). Notably,
4-phenylpentenoic acid gave the corresponding lactone in
moderate yield, whereas only a rearrangement product due to
1,2-phenyl migration was isolated in the TfOH-catalyzed
lactonizations using PhI(OAc)2 as the oxidant.8 5-Hexenoic
acid and 6-heptenoic acid failed to afford the corresponding
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Note
Figure 1. In situ 1H NMR monitoring of the dioxygenation of 1-octene and ring opening of 1,2-epoxyoctane with peracetic acid in acetic acid in the
presence of Ac2O (1,2-dimethoxyethane as internal standard) at room temperature: (A) no catalyst; (B) 10 mol % of TfOH (No epoxide observed);
(C) no catalyst; and (D) 10 mol % of TfOH (1,1-diacetoxyoctane generated via Meinwald rearrangement).
lactones but yielded the linear diacetoxylation products instead
(entries 4 and 5).
EXPERIMENTAL SECTION
■
Preparation of Peracetic Acid Solution (1.0 M). Peracetic acid
(35.5%, 10 g, 46 mmol) was diluted with glacial acetic acid (10 mL)
with the cooling of an ice−water bath, followed by the dropwise
addition of 20 g of acetic anhydride under gentle shaking (CAUTION!
exothermic reaction). This mixture was diluted with glacial acetic acid
to a level of 1.0 M AcO2H. The resulting solution of AcO2H was
stored at 4 °C (solidified) and warmed to room temperature before
using.
General Procedure for TfOH-Catalyzed Diacetoxylation of
Alkenes Using AcO2H. The solution of peracetic acid (1.0 M, 2
mmol) was added to a 10 mL glass vial charged with 1.0 mmol of
aliphatic alkene and cooled with the aid of a water bath (for aromatic
alkenes, cooled in an ice−water bath), followed by the addition of 1.0
M TfOH solution in glacial acetic acid (0.1 mmol). The resulting
reaction mixture was stirred at room temperature for required time.
The reaction mixture was concentrated by rotary evaporation, and the
residue was used to determine the diastereoselectivity by NMR if
applicable. The crude product was purified by column chromatography
on silica gel using hexane and ethyl acetate as the eluent.
A mechanism is proposed in Scheme 3. Whether catalytic or
not, the dioxygenations described in this work pass through the
cascade epoxidation/ring-opening of alkenes followed by
acetylation. TfOH plays a dual role as catalyst for the ring-
opening of the epoxide as well as following acetylation of the
hydroxyl group. The reaction mechanism proposed by Afonso
et al. suggests the fast formation of the epoxide catalyzed by
PTSA via its corresponding peroxysulfonic acid.11 In our case,
there was no obvious catalytic effect of TfOH in epoxidation
step. In the subsequent ring-opening of epoxides, both SN2- and
SN1-type substitutions may take place, depending on the
substituent R1. If the latter stabilizes a carbocationic
intermediate, ring-opening substitution mainly passes through
a SN1 pathway giving rise to the observed low diastereose-
lectivity.
In conclusion, we have described a metal-free, clean, and
cheap diacetoxylation method for alkenes catalyzed by triflic
acid using commercially available peroxyacids as oxidant. The
simple and convenient operation together with its high
efficiency and wide scope of alkenes render this method a
viable and complementary alternative to the well-established
osmium-catalyzed dihydroxylation of alkenes.
General Procedure for TfOH-Catalyzed Diacetoxylation of
Alkenes Using m-CPBA. 3-Chloroperoxybenzoic acid (>70%) was
added to the solution of alkene (1.0 mmol) in glacial acetic acid (2
mL) in a 10 mL glass vial cooled by a water bath (for aromatic alkenes,
cooled in an ice−water bath), followed by the addition of 1.0 M TfOH
solution in glacial acetic acid (0.1 mmol). The resulting reaction
mixture was stirred at room temperature for required time, followed by
the addition of 0.5 mL of acetic anhydride. This reaction mixture was
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Note
a
Table 2. TfOH-Catalyzed Diacetoxylation of Alkenes Using Peroxyacids as Oxidants
a
Conditions: 1.0 mmol of alkene, 2.0 mmol of AcO2H [1 M in AcOH−Ac2O (2.2/1 v/v)], room temperature. See Experimental Section for details.
Isolated yields. The yields in parentheses obtained from the reactions using 2.0 mmol of m-CPBA instead of AcO2H in AcOH and then treated with
b
c
d
e
Ac2O. dr refers to diastereoselectivity (syn/anti). Carried out at 50 °C. 3 equiv of AcO2H used.
a
Table 3. TfOH-Catalyzed Lactonization of Alkenes Using Peroxyacids as Oxidants
a
Conditions: 1.0 mmol of alkene, 2.0 mmol of AcO2H [1 M in AcOH−Ac2O (2.2/1 v/v)], room temperature. See the Experimental Section for
b
details. Isolated yields. The yield in parentheses was obtained from the reaction using 2.0 mmol of m-CPBA instead of AcO2H. The reaction
mixture was treated with Ac2O.
stirred for 12 h and concentrated by rotary evaporation and the residue
was used to determine the diastereoselectivity by NMR if applicable.
The residue was further diluted by dichloromethane and washed with
10% NaOH solution, dried over Na2SO4, concentrated, and purified by
column chromatography on silica gel using hexane, ethyl acetate as the
eluent.
1,2-Diacetoxyoctane (5a).8 Colorless oil. 1H NMR (600 MHz,
CDCl3): δ 5.08−5.04 (m, 1.0 H), 4.21 (dd, J = 12.0, 3.0 Hz, 1.0 H),
4.02 (dd, J = 12.0, 6.6 Hz, 1.0 H), 2.06 (s, 3.0 H), 2.05 (s, 3.0 H),
1.59−1.52 (m, 2.0 H), 1.30−1.25 (m, 8.0 H), 0.87 (t, J = 7.2 Hz, 3.0
H). 13C NMR (150 MHz, CDCl3): δ 170.8, 170.6, 71.6, 65.1, 31.6,
30.7, 29.0, 25.0, 22.5, 21.1, 20.8, 14.0.
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Note
1,2-Diacetoxy-3-phenylethane (5h).8 Colorless oil. 1H NMR (600
MHz, CDCl3): δ 7.37−7.31 (m, 5H), 6.01 (dd, J = 8.4, 3.6 Hz, 1H),
4.33 (dd, J = 12.0, 3.6 Hz, 1H), 4.29 (dd, J = 8.4, 12.0 Hz, 1H), 2.12
(s, 3H), 2.06 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 170.7, 170.1,
136.5, 128.6, 128.6, 126.7, 73.3, 66.1, 21.1, 20.8.
Scheme 3. Proposed Dual Catalytic Role of TfOH in the
Diacetoxylation of Alkenes Using AcO2H
1,2-Diacetoxy-3-(4-fluorophenyl)ethane (5i).9a Colorless oil. 1H
NMR (600 MHz, CDCl3): δ 7.36−7.33 (m, 2 H), 7.08−7.04 (m, 2
H), 5.98 (dd, J = 13.8, 4.2 Hz, 1 H), 4.30 (dd, J = 12.0, 4.2 Hz, 1H,
4.26 (dd, J = 12.0, 7.8 Hz, 1H), 2.11 (s, 3 H), 2.05 (s, 3 H). 13C NMR
(150 MHz, CDCl3): δ 170.6, 170.0, 163.6, 161.9, 132.4, 132.4, 128.6,
128.6, 115.7, 115.6, 72.6, 65.9, 65.9, 21.1, 20.7.
anti-1,2-Diacetoxy-1,2-diphenylethane (anti-5j).8 The colorless
1
oil slowly solidified to a solid. H NMR (600 MHz, CDCl3): δ 7.29−
7.28 (m, 6 H), 7.20−7.19 (m, 4 H), 6.08 (s, 2 H), 2.01 (s, 6 H). 13C
NMR (150 MHz, CDCl3): δ 169.6, 134.0, 128.4, 128.1, 127.6, 76.4,
21.0.
syn-1,2-Diacetoxy-1,2-diphenylethane (syn-5j).8 The colorless oil
slowly solidified to a solid. 1H NMR (600 MHz, CDCl3): δ 7.22−7.14
(m, 10 H), 6.05 (s, 2 H), 2.08 (s, 6 H). 13C NMR (150 MHz, CDCl3):
δ 169.8, 136.1, 128.4, 128.2, 127.5, 77.1, 21.0.
3-Acetoxy-γ-butyrolactone (6a).10 Colorless oil. 1H NMR (600
MHz, CDCl3): δ 5.41−5.42 (m, 1 H), 4.49 (dd, J = 4.8, 11.4 Hz, 1 H),
4.35 (d, J = 10.8 Hz, 1 H), 2.84 (dd, J = 6.6, 18.0 Hz, 1 H), 2.60 (d, J =
18.0 Hz, 1 H), 2.08 (s, 3 H). 13C NMR (150 MHz, CDCl3): δ 174.5,
170.3, 73.0, 69.7, 34.5, 20.8.
1,2-Diacetoxydecane (5b).9a Colorless oil. H NMR (600 MHz,
1
8
1
ω-Acetoxy-γ-pentanolactone (6b). Colorless oil. H NMR (600
MHz, CDCl3): δ 4.75−4.71 (m, 1 H), 4.30 (dd, J = 3, 12 Hz, 1 H),
4.13 (dd, J = 5.4, 12.6 Hz, 1 H), 2.62−2.52 (m, 2 H), 2.37−2.32 (m, 1
H), 2.09 (s, 3 H), 2.07−2.00 (m, 1 H). 13C NMR (150 MHz, CDCl3):
δ 176.5, 170.6, 77.2, 65.3, 28.1, 23.9, 20.9.
CDCl3): δ 5.06−5.05 (m, 1 H), 4.21 (dd, J = 3.0, 12.0 Hz), 4.02 (dd, J
= 6.6, 11.4 Hz), 2.06 (s, 3 H), 2.05 (s, 3 H), 1.57−1.55 (m, 2 H),
1.30−1.25 (m, 12 H), 0.87 (t, J = 11.4 Hz, 3 H). 13C NMR (150 MHz,
CDCl3): δ 170.8, 170.6, 71.6, 65.1, 31.8, 30.7, 29.4, 29.3, 29.1, 25.1,
22.6, 21.1, 20.8, 14.1.
ω-Acetoxyl-4-phenyl-γ-pentanolactone (6c). Colorless oil. 1H
NMR (600 MHz, CDCl3): δ 7.40−7.33 (m, 5 H), 4.32 (d, J = 12
Hz, 1 H), 4.29 (d, J = 12 Hz, 1 H), 2.76−2.66 (m, 2 H), 2.58−2.52
(m, 1 H), 2.49−2.44 (m, 1 H), 2.08 (s, 3 H). 13C NMR (150 MHz,
CDCl3): δ 175.9, 170.3, 139.8, 128.8, 128.5, 124.9, 86.7, 69.6, 31.2,
28.8, 20.7. HRMS (ESI): calcd for C13H15O4 [M + H]+ 235.0965,
found 235.0962. IR (neat): 3545, 3474, 3062, 3031, 2957, 2924, 2854,
1790, 1743, 1450, 1326, 1254, 1049, 949, 767 cm−1.
1,2-Diacetoxytetradecane (5c). Colorless oil. 1H NMR (600 MHz,
CDCl3): δ 5.05−5.04 (m, 1 H), 4.20 (dd, J = 3.0, 12.0 Hz), 4.00 (dd, J
= 6.6, 11.4 Hz), 2.04 (s, 3 H), 2.04 (s, 3 H), 1.56−1.54 (m, 2 H),
1.27−1.23 (m, 20 H), 0.86 (t, J = 6.6 Hz, 3 H). 13C NMR (150 MHz,
CDCl3): δ 170.8, 170.6, 77.2, 77.0, 76.8, 71.5, 65.1, 31.9, 30.6, 29.6,
29.6, 29.6, 29.5, 29.4, 29.3, 29.3, 25.1, 22.6, 21.0, 20.7, 14.1. HRMS
(ESI): calcd for C18H34NaO4 [M + Na]+ 337.2349, found 337.2346.
IR (neat): 2926, 2855, 1745, 1462, 1371, 1227, 1049 cm−1.
1,2-Diacetoxyoctadecane (5d). The colorless oil slowly solidified
5,6-Diacetoxyhexanoic Acid (6d).8 Colorless oil. H NMR (600
1
MHz, CDCl3): δ 5.10−5.06 (m, 1 H), 4.22 (dd, J = 12.0, 3.6 Hz, 1 H),
4.04 (dd, J = 12.0, 6.6 Hz, 1 H), 2.39 (t, J = 6.6 Hz, 2 H), 2.07 (s, 3
H), 2.06 (s, 3 H), 1.73−1.62 (m, 4 H).13C NMR (150 MHz, CDCl3):
δ 178.5, 170.8, 170.7, 71.0, 64.9, 33.4, 30.0, 21.0, 20.8, 20.2.
1
to a hard white waxlike solid. H NMR (600 MHz, CDCl3): δ 5.08−
5.04 (m, 1 H), 4.21 (dd, J = 3.0, 12.0 Hz), 4.02 (dd, J = 6.6, 12.0 Hz),
2.063 (s, 3 H), 2.058 (s, 3 H), 1.60−1.52 (m, 2 H), 1.30−1.25 (m, 28
H), 0.87 (t, J = 7.2 Hz, 3 H). 13C NMR (150 MHz, CDCl3): δ 170.9,
170.7, 71.6, 65.1, 31.9, 30.7, 29.7, 29.7, 29.7(2C), 29.6(2C), 29.6, 29.5,
29.4, 29.4, 29.4, 25.1, 22.7, 21.1, 20.8, 14.1. HRMS (ESI): calcd for
C22H42NaO4 [M + Na]+ 393.2975, found 393.2973. IR (neat): 3295,
2916, 2849, 1745, 1720, 1463, 1263 cm−1.
8
1
6,7-Diacetoxyheptanoic Acid (6e). Colorless oil. H NMR (600
MHz, CDCl3): δ 5.09−5.05 (m, 1 H), 4.21 (dd, J = 12.0, 3.6 Hz, 1 H),
4.02 (dd, J = 12.0, 6.0 Hz, 1 H), 2.36 (t, J = 7.2 Hz, 1 H), 2.064 (s, 3
H), 2.058 (s, 3 H), 1.67−1.58 (m, 4 H), 1.41−1.36 (m, 2 H). 13C
NMR (150 MHz, CDCl3): δ 179.1, 170.8, 170.7, 71.2, 65.0, 33.6, 30.3,
24.5, 24.3, 21.0, 20.8.
1,2-Diacetoxy-3-phenylpropane (5e).8 Colorless oil. 1H NMR
(600 MHz, CDCl3): δ 7.30−7.19 (m, 5H), 5.26 (ddd, J = 3.6, 6.6, 13.2
Hz, 1H), 4.23 (dd, J = 12.0, 3.6 Hz, 1H), 4.02 (dd, J = 12.6, 6.0 Hz,
1H), 2.93 (dd, J = 13.8, 7.2 Hz, 1H), 2.88 (dd, J = 13.8, 6.6 Hz, 1H),
2.07 (s, 3H), 2.02 (s, 3H). 13C NMR (150 MHz, CDCl3): δ 170.7,
170.3, 136.2, 129.2, 128.5, 126.8, 77.2, 77.0, 76.8, 72.0, 64.2, 37.0, 20.9,
20.7.
ASSOCIATED CONTENT
■
S
* Supporting Information
General experimental conditions and 1H and 13C NMR spectra
for all compounds. This material is available free of charge via
the Internet at http://pubs.acs.org.
1,2-Diacetoxytetrahydronaphthalene (5f).8 (1:1 mixture of syn
1
and anti). Colorless oil. H NMR (600 MHz, CDCl3): δ 7.28−7.14
(m, 8 H), 6.18 (d, J = 3.0 Hz, 1 H), 6.07 (d, J = 6.0 Hz, 1.0 H), 5.25
(dt, J = 10.8, 3.6 Hz, 1 H), 5.18 (ddd, J = 9.2, 6.0, 3.3 Hz,1 H), 3.03
(dt, J = 16.8, 5.4 Hz,1 H), 2.95−2.90 (m, 3 H), 2.27−2.21 (m, 1 H),
2.20−2.15 (m, 1 H), 2.11 (s, 3.0 H), 2.10 (s, 3 H), 2.06 (s, 0.6 H),
2.05 (s, 3.0 H), 2.07−1.94 (m, 2 H). 13C NMR (150 MHz, CDCl3): δ
170.6, 170.6, 170.4, 170.3, 136.6, 136.4, 132.7, 132.7, 130.0, 129.1,
128.8, 128.7, 128.6, 128.3, 126.5, 126.4, 71.4, 71.0, 70.1, 69.3, 27.1,
25.7, 24.9, 23.3, 21.2, 21.1, 21.1.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: lutz.gade@uni-hd.de.
ACKNOWLEDGMENTS
■
anti-1,2-Diacetoxycyclohexane (5g).13 Colorless oil. 1H NMR
(600 MHz, CDCl3): δ 4.81−4.76 (m, 2 H), 2.08−2.02 (m, 2 H), 2.01
(s, 6H), 1.72−1.70 (m, 2H), 1.39−1.24 (m, 4H). 13C NMR (150
MHz, CDCl3): δ 170.5, 73.7, 30.1, 23.4, 21.1.
Y.-B. Kang works at CaRLa of the University of Heidelberg,
cofinanced by the University of Heidelberg, the state of Baden-
Wurttemberg, and BASF SE. Support from these institutions is
̈
gratefully acknowledged.
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The Journal of Organic Chemistry
Note
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