Palladium-catalyzed hydroamination of C-(tetra-O-acetyl-β-d- galactopyranosyl)allene

Article abstract of DOI:10.1016/j.carres.2010.11.006

Both palladium(0) and palladium(II) methods for catalyzed hydroamination of C-(tetra-O-acetyl-β-d-galactopyranosyl)allene with a variety of aromatic amines have been successfully developed. Copyright

Full text of DOI:10.1016/j.carres.2010.11.006

Carbohydrate Research 346 (2011) 334–339
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Note
Palladium-catalyzed hydroamination of
C-(tetra-O-acetyl-b-D-galactopyranosyl)allene
⇑
Chaleowsak Khamwong, Uthai Sakee
Center of Excellence for Innovation in Chemistry (PERCH-CIC), Department of Chemistry, Faculty of Science, Mahasarakham University, Mahasarakham 44150, Thailand
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 June 2010
Received in revised form 4 November 2010
Accepted 8 November 2010
Available online 9 December 2010
Both palladium(0) and palladium(II) methods for catalyzed hydroamination of C-(tetra-O-acetyl-b-D-
galactopyranosyl)allene with a variety of aromatic amines have been successfully developed.
Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.
Keywords:
Hydroamination
Amine
Palladium
Allene
Galactopyranosyl
The amine functionality is one of the most ubiquitous in organic
chemistry. Its importance is exemplified by the diversity of mole-
cules that contain this functional group, which includes natural
products and pharmacological agents.1 For this reason C–N bond
formation is of great interest, which is apparent from the number
of methodologies that have been developed for this purpose.2
Hydroamination, the formal addition of an N–H bond across a
C@C unsaturated bond, is a highly desirable and an atom-econom-
ical process for the preparation of amine derivatives.2d,3 Allenes
constitute an important class of organic compounds with unusual
chemical properties due to the cumulated double bond.4 The cata-
lytic hydroamination of allenes should be a straightforward meth-
od for the synthesis of allylamines. The intramolecular
hydroamination of amino allenes is catalyzed by organolantha-
nide5 Group 4 early transition-metal complexes,6 and late transi-
tion-metal (Pd, Ag, Au) complexes.2b,7 Only a small number of
catalytic intermolecular hydroamination reactions of allenes have
been reported.8 We report herein on the palladium-catalyzed
acid (TFA), the mixture of desired allylic amine 5 (29%) and a minor
amount (18%) of dienic amine was obtained (entry 1 in Table 1).
The reaction conditions were adjusted to find a suitable cata-
lyst–ligand–solvent–carboxylic acid system for the desired trans-
formation. The results are summarized in Table 1. These results
suggested that both Pd(0) and Pd(II) catalysts and carboxylic acid
play a dramatic part on the yields of the desired allelic amine 5.
In addition, a profound solvent effect on the reaction was observed.
THF was found to be the best solvent (Table 1, entry 18).
Under the optimized reaction conditions [Pd(OAc)2 was used as
a catalyst, TFA as the carboxylic acid and THF as the solvent], a ser-
ies of amines were tested in the reaction, and the results are sum-
marized in Table 2.
A possible reaction pathway for Pd(0)-catalyzed hydroamination
is showed in Scheme 2. The two principal mechanistic pathways to
be considered for hydroamination involve either activation of the
amine (part a) or palladacycle formation (path b). The oxidative
addition of carboxylic acid to Pd(0) produced hydridopalladium(II)
intermediate species (I), which on reaction with amine would give
intermediate (III) and carboxylic acid. Species III would form the
hydroamination of a C-(tetra-O-acetyl-b-
(1) with amines in the presence of a carboxylic acid. Initially the
reaction of C-(tetra-O-acetyl-b- -galactopyranosyl)allene (1) with
D-galactopyranosyl)allene
D
p-allylpalladium intermediate (VIII) with C-(tetra-O-acetyl-b-D-
aniline (2) using Yamamoto’s conditions (5 mol % Pd2(dba)3ÁCHCl3,
10 mol % Ph3P, 20 mol % CH3COOH in THF at 60 °C for 24 h) was
studied.8f Quite unexpectedly, a mixture of diallylated acetate 3
and diallylated amine 4 was obtained in 35% and 10% yields,
respectively, along with trace amounts of 5 (Scheme 1). When
the same reaction was carried out in the presence of trifluoroacetic
galactopyranosyl)allene (1) which, after reductive elimination,
would give the hydroamination product (IX). The formation of
diallylated acetate (VII) and diallylated amine (XII) could arise by
a combination of either path a or path b, intermediate (V, X)
(Scheme 2, path a) and intermediate (II) (Scheme 2, path b).
On the other hand, hydroamination of C-(tetra-O-acetyl-b-D-
galactopyranosyl)allene (1) gave a yield of 42% allylic amine 5
using Pd(OAc)2 and TFA in THF (Table 1, entry 18). The two possible
mechanistic pathways to be considered for hydroamination
⇑
Corresponding author. Tel./fax: +66 43 754246.
E-mail address: uthai.s@msu.ac.th (U. Sakee).
0008-6215/$ - see front matter Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2010.11.006

C. Khamwong, U. Sakee / Carbohydrate Research 346 (2011) 334–339
335
OAc
OAc
OAc
OAc
OAc
OAc
O
AcO
AcO
AcO
AcO
O
C
O
AcO
OAc
NHPh
OAc
5 mol % Pd2(dba)3 CHCl3
AcO
10 mol % Ph3P,
20 mol % CH3COOH
THF, 60 °C, 24 h
+
1
+
OAc
AcO
OAc
O
O
PhNH2
2
OAc
OAc
AcO
AcO
3
+
4
OAc
OAc
O
NHPh
AcO
OAc
5
Scheme 1. Palladium-catalyzed hydroamination of C-(tetra-O-acetyl-b-D-galactopyranosyl)allene.
Table 1
Effect of reaction parameters on hydroamination of C-(tetra-O-acetyl-b-D-galactopyranosyl)allene (1)a with anilineb
Entry
Palladium salt and ligand (mol %)
Carboxylic acid and additive (mol %)
Solvent
Temperature (°C)
% Yieldc
5
4
1
2
3
4
5
6
7
8
Pd2(dba)3ÁCHCl3 (5), Ph3P (10)
Pd2(dba)3ÁCHCl3 (5), Ph3P (10)
Pd2(dba)3 (5), Ph3P (10)
Pd2(dba)3 (5), Ph3P (10)
Pd2(dba)3 (5), TFP (10)
Pd2(dba)3 (5), Ph3P (10)
Pd2(dba)3 (5), Ph3P (10)
Pd(OAc)2 (5), Ph3P (20)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (10)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd2(dba)3 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
TFA (20)
TFA (20)
TFA (20)
TFA (20)
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DMF
CH3CN
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
DCM
CH3CN
Toluene
Dioxane
60
rt
60
rt
rt
rt
rt
rt
rt
60
60
rt
rt
rt
rt
rt
rt
rt
60
rt
rt
60
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
29
10
15
13
6
ND
ND
6
18
46
42
42
47
14
17
48
12
12
26
13
10
7
13
17
14
12
9
9
3
5
13
19
12
ND
ND
16
14
14
15
9
TFA (20)
Formic acid (20)
Benzoic acid (20)
TFA (20)
TFA (20)
TFA (20)
TFA (20)
TFA (50)
TFA (100)
TFA (10)
TFA (5)
TFA (5)
TFA (5)
TFA (20)
TFA (20)
Acetic acid (20)
—
—
9
21
23
14
25
22
13
15
ND
8
42
32
25
17
12
21
25
17
31
32
31
30
33
24
14
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Pd(OAc)2 (5)
Pd(OAc)2 (10)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
TFA (20)
TFA (20), K2S2O8 (250)
TFA (20), K2S2O8 (100)
TFA (20), LiCl (200)
LiCl (200)
TFA (50)
TFA (20)
TFA (20)
TFA (20)
TFA (20)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
ND = Not detected.
a
C-(Tetra-O-acetyl-b-D
-galactopyranosyl)allene (1) was prepared according to the literature method.9
All reactions were carried out with conditions: C-(tetra-O-acetyl-b-D-galactopyranosyl)allene (1) (0.27 mmol) and aniline (0.81 mmol) in 0.5 mL of solvent for 24 h.
Isolated yields.
b
c
involve either activation of the amine or activation of the allene. In
the allene activation (Scheme 3, path c) the CH2@C double bond of
allene is activated by coordination to the palladium, and the C–N
bond is formed by nucleophilic attack of amine on the coordinate
allene. To liberate the product, the palladium–carbon bond in the
resulting ammonioallyl complex has to be cleaved. This can be
brought about either by direct protonolysis or by protonation at
the palladium with subsequent C–H reductive elimination. Amine
activation (Scheme 3, path d) proceeds via oxidative addition of
the amine N–H bond to the coordinatively unsaturated palladium
center, forming the amido hydrido complex, followed by allene
coordination, insertion of the allene into the palladium–nitrogen

336
C. Khamwong, U. Sakee / Carbohydrate Research 346 (2011) 334–339
Table 2
Hydroamination of C-(tetra-O-acetyl-b-D-galactopyranosyl)allene (1) with aromatic aminesa
OAc
OAc
OAc
OAc
OAc
O
OAc
O
NHR
5 mol % Pd(OAc)2
AcO
AcO
OAc
C
O
AcO
AcO
OAc
OAc
NHR
20 mol % TFA
THF, tr, 24 h
+
1
+
7a-d
AcO
O
OAc
8a−d
RNH2
6a−d
AcO
Entry
Amine
Productb (%)
NH2
1
7a (16)
8a (ND)
OMe
6a
NH2
2
7b (22)
8b (ND)
NO2
6b
NH2
3
4
7c (25)
7d (17)
8c (3)
8d (6)
NO2
NH2
6c
6d
ND = Not detected.
a
Reaction conditions: C-(tetra-O-acetyl-b-D-galactopyranosyl)allene (1) (0.27 mmol); amine (0.81 mmol); Pd(OAc)2 (5 mol %); TFA (20 mol %);THF (0.5 mL); room tem-
perature for 24 h.
b
Isolated yields.
bond, and finally C–H reductive elimination, liberating the product
and closing the catalytic cycle.
In conclusion, we have successfully developed both Pd(0)- and
Pd(II)-catalyzed methods for hydroamination of C-(tetra-O-
d = doublet, dd = doublet of doublets, t = triplet, m = multiplet, br
s = broad singlet, app. t = apparent triplet. C-(Tetra-O-acetyl-b-
galactopyranosyl)allene [(1S)-2,3,4,6-(tetra-O-acetyl-1,5-anhydro-
D-
1-C-propadienyl-D-galactitol, 1] was prepared according to the
acetyl-b-
D-galactopyranosyl)allene (1) with a variety of aromatic
literature method.9
amines.
1.2. Typical general procedure
1. Experimental
All reactions were carried out in an atmosphere of air. A reac-
tion tube was charged with the C-(tetra-O-acetyl-b-D-galactopyr-
1.1. General methods
anosyl)allene (1) (0.5 mmol), amines (1.5 mmol), Pd salts
(catalyst, 5–10 mol %), Ph3P (ligand, 5 mol %), carboxylic acid (10–
100 mol %), LiCl or LiBr (additive, 5 mol %), and solvent (1 mL/
mmol). The mixture was either stirred at room temperature or
heated at 60 °C for 24 h, then the solvent was evaporated under re-
duced pressure, and the residue was purified by flash column chro-
matography on silica gel to give the product.
All reagents were commercially available and used without
purification. Flash column chromatography was performed using
Silica Gel 60 (230–400 mesh). Accurate molecular masses were re-
corded on a micrOTOF machine. Infrared spectra were recorded
using a Perkin–Elmer FTIR spectrometer. The IR samples were pre-
pared as thin films by evaporation of a solution of the compound in
CH2Cl2 onto a germanium plate. Nuclear magnetic resonance spec-
tra were determined at 400 MHz (1H) and at 100 MHz (13C) on Bru-
ker spectrometers. Chemical shift values are quoted in parts per
million (ppm) downfield from TMS, and coupling constants are in
Hertz. Chemical shift multiplicities are reported as s = singlet,
1.2.1. Data for 3
IR (film) cmÀ1: 3477, 2964, 1747, 1436, 1372, 1229, 1119, 1049;
1H NMR (CDCl3): d 5.92 (1H, d, J 6.4), 5.80 (1H, d, J 6.0), 5.41–5.45
(2H, m), 5.31–5.36 (2H, m), 5.24 (1H, t, J 2.4), 5.21 (1H, t, J 3.6), 5.15

C. Khamwong, U. Sakee / Carbohydrate Research 346 (2011) 334–339
337
S
(V)
RCOO
S
PdII
S
C
S
S
(VII)
O
(IV)
S
OOR
S
PdII
RCOO
(VI)
O
R
S
C
RCO2H
S
RCO2H
S
R'NH2
R'
C
O
RCO2H
Path a
HN PdII
(III)
H
S
Pd0
S
R
(II)
O
(I)
PdII
H
Path b
PdII
C
R'NH2
S
(VIII)
S
R'NH
PdII
S
S
NHR'
S
NHR'
(IX)
(XII)
S
C
S
R'NH
PdII
(X)
S = C-(tetra-O-acetyl-β-D-galactopyranosyl)-
Scheme 2. Proposed mechanistic pathways for palladium(0)-catalyzed hydroamination.
part c
part d
S
S
NHR'
R'NH2
C
R'NH2
NH2R'
PdII
R'NH2
[PdII]
H
S
C
S
NHR'
H
[Pd]
H
PdII
NH2R'
[Pd] NHR'
S
H
Pd
[Pd] NHR'
S
S
C
C
R'NH2
S
NHR'
H
S = C-(tetra-O-acetyl-β-D-galactopyranosyl)-
Scheme 3. Proposed mechanistic pathways for palladium(II)-catalyzed hydroamination.

338
C. Khamwong, U. Sakee / Carbohydrate Research 346 (2011) 334–339
(1H, t, J 6.4), 5.03–5.06 (2H, m), 4.82 (1H, d, J 13.2), 4.02–4.20 (6H,
m), 1.90–2.20 (30H, 10 Â s); 13C NMR (CDCl3): d 170.42, 170.32,
170.29, 170.15, 170.11, 170.01, 169.96, 169.82, 169.57, 145.01,
143.28, 123.86, 120.77, 69.62, 68.88, 68.76, 68.40, 68.24, 68.20,
67.98, 67.85, 67.82, 67.44, 61.67, 61.32, 59.27, 20.70, 20.66,
20.64, 20.60, 15.61; HRMS: calcd for C36H48O20Na (M+Na): m/z
823.2637; found: m/z 823.2566.
45.31, 20.72, 20.69, 20.66; HRMS: calcd for C23H28N2O11Na
(M+Na): m/z 531.1591; found: m/z 531.1668.
1.2.7. Data for 8c
IR: (film) cmÀ1: 3736, 2362, 1744, 1540, 1370, 1225, 1023; 1H
NMR (CDCl3): d 7.53 (1H, d, J 6.4), 7.41 (1H, app. t, J 2.4 and 2.0),
7.27 (1H, s), 6.89 (1H, d, J 2.0), 5.91 (1H, d, J 7.2), 5.40–5.46 (3H,
m), 5.27–5.31 (2H, m), 5.22–5.26 (2H, m) 5.12–5.18 (4H, m),
4.01–4.15 (6H, m), 2.00–2.13 (27H, 9 Â s); 13C NMR (CDCl3): d
170.61, 170.52, 170.44, 170.19, 170.05, 170.01, 169.96, 169.91,
149.44, 148.82, 144.33, 142.93, 129.74, 123.26, 118.69, 117.18,
112.09, 106.16, 70.07, 69.06, 69.02, 68.16, 67.96, 67.73, 67.59,
61.85, 61.63, 42.34, 20.80, 20.75, 20.70, 20.65, 14.12; HRMS: calcd
for C40H50N2O20Na (M+Na): m/z 901.2855; found: m/z 901.2904.
1.2.2. Data for 4
IR (film) cmÀ1: 3440, 2361, 1747, 1637, 1372, 1226, 1023; 1H
NMR (CDCl3): d 7.16 (2H, app. t, J 8 and 7.6), 6.68–6.72 (1H, m),
6.58 (2H, d, J 8.4), 5.83 (1H, d, J 6.8), 5.75 (1H, d, J 6.4), 5.41–5.45
(2H, m), 5.28–5.34 (2H, m), 5.21–5.26 (2H, m), 5.10–5.14 (3H,
m), 5.00 (1H, app. t, J 6.4 and 5.6), 4.00–4.20 (6H, m), 1.80–2.10
(27H, 9 Â s); 13C NMR (CDCl3): d 170.54, 170.41, 170.13, 170.09,
169.98, 169.90, 169.83, 169.81, 147.84, 144.58, 129.34, 129.24,
121.82, 120.62, 117.82, 112.75, 69.48, 69.06, 68.77, 68.36, 68.26,
68.10, 67.99, 67.91, 67.52, 61.82, 61.51, 42.14, 20.78, 20.75,
1.2.8. Data for 7d
IR (film) cmÀ1: 3440, 2361, 1748, 1584, 1533, 1372, 1228, 1050,
773; 1H NMR (CDCl3): d 7.83–7.86 (1H, m), 7.77–7.82 (1H, m),
7.45–7.53 (2H, m), 7.36 (1H, d, J 7.6), 7.30 (1H, d, J 6.8), 6.61 (1H,
d, J 7.2), 6.12 (1H, dt, J 15.6 and 5.2), 5.93 (1H, q, J 15.6 and 5.2),
5.38 (1H, d, J 3.2), 5.33 (1H, dd, J 10.4 and 5.6), 5.14 (1H, dd, J
10.4 and 3.2), 4.83 (1H, t, J 3.2), 4.07–4.15 (3H, m), 4.05 (2H, d, J
5.2), 1.90–2.13 (12H, 4 Â s); 13C NMR (CDCl3) d: 170.58, 170.20,
170.05, 169.88, 142.73, 134.34, 133.99, 128.71, 126.45, 125.79,
124.86, 123.99, 123.53, 119.84, 117.95, 105.02, 72.50, 68.39,
68.33, 68.04, 68.01, 61.87, 45.94, 20.72, 20.70, 20.66; HRMS: calcd
for C27H31NO9Na (M+Na): m/z 536.1897; found: m/z 536.1963.
20.73, 20.67, 20.65, 15.87; HRMS: calcd for
C40H51NO18Na
(M+Na): m/z 856.3004; found: m/z 856.3036.
1.2.3. Data for 5
IR (film) cmÀ1: 3418, 2361, 1746, 1633, 1604, 1507, 1371, 1226,
1051; 1H NMR (CDCl3): d 7.17 (2H, app. t J 8.4 and 7.2), 6.71 (1H,
app. t J 8.4 and 7.2), 6.60 (2H, d, J 7.6), 5.98 (1H, dt, J 15.6 and
5.2), 5.82 (1H, q, J 15.6 and 5.2), 5.37 (1H, d, J 3.2), 5.28 (1H, dd, J
10.4 and 5.6), 5.10 (1H, dd, J 10.4 and 3.2), 4.80 (1H, t, J 3.2),
4.00–4.14 (3H, m), 3.84 (2H, d, J 5.2) 1.90–2.10 (12H, 4 Â s); 13C
NMR (CDCl3) d: 170.52, 170.19, 170.06, 169.87, 147.64, 134.47,
129.27, 123.49, 117.87, 113.14, 72.53, 68.31, 68.29, 68.01, 61.83,
45.62, 20.73, 20.69, 20.66; HRMS: calcd for C23H30NO9 (M+H):
m/z 464.1921; found: m/z 464.1968.
1.2.9. Data for 8d
IR (film) cmÀ1: 3442, 2362, 2066, 1746, 1638, 1372, 1227, 1048;
1H NMR (CDCl3): d 7.83 (1H, d, J 8.8), 7.77 (1H, d, J 7.6), 7.35–7.46
(2H, m), 7.33 (1H, d, J 7.6), 7.24 (1H, d, J 8.4), 6.59 (1H, d, J 7.6), 5.94
(1H, d, J 7.2), 5.40–5.45 (3H, m), 5.31–5.36 (3H, m), 5.22–5.30 (2H,
m), 5.16–5.21 (3H, m), 4.02–4.25 (6H, m), 1.90–2.10 (27H, 9 Â s);
1.2.4. Data for 7a
13C NMR (CDCl3):
d 170.64, 170.56, 170.51, 170.47, 170.23,
IR (film) cmÀ1: 3442, 2362, 1747, 1638, 1515, 1372, 1231, 1023;
1H NMR (CDCl3): d 6.79 (2H, d, J 8.8), 6.60 (2H, d, J 8.8), 5.97 (1H, dt,
J 15.6 and 5.2), 5.85 (1H, q, J 15.6 and 5.2), 5.42 (1H, d, J 3.2), 5.29
(1H, dd, J 10.4 and 5.6), 5.12 (1H, dd, J 10.4 and 3.2), 4.79 (1H, t, J
3.2), 4.00–4.10 (3H, m), 3.80 (2H, d, J 5.2), 1.90–2.10 (15H, 5 Â s);
170.20, 170.12, 170.03, 145.22, 143.30, 134.36, 134.26, 129.29,
128.99, 128.67, 128.48, 126.54, 125.84, 122.82, 120.39, 117.79,
104.13, 69.60, 69.14, 69.07, 68.56, 68.40, 68.28, 67.90, 67.86,
67.70, 61.68, 61.64, 61.14, 43.52, 20.69, 20.67, 20.63, 14.12; HRMS:
calcd for
906.3220.
C44H53NO18Na (M+Na): m/z 906.3160; found: m/z
13C NMR (CDCl3):
d 170.53, 170.23, 170.13, 170.08, 152.44,
141.82, 134.79, 123.41, 114.92, 114.57, 72.50, 68.40, 68.33, 68.04,
68.01, 61.87, 45.94, 20.72, 20.70, 20.66; HRMS: calcd for
Acknowledgments
C24H31NO10Na (M+Na): m/z 516.1846; found: m/z 516.2006.
This work was financially supported by PERCH-CIC and
Mahasarakham University.
1.2.5. Data for 7b
IR (film) cmÀ1: 3439, 2362, 1747, 1636, 1604, 1474, 1372, 1312,
1228, 1113, 1048; 1H NMR (CDCl3): d 8.09 (2H, d, J 8.8), 6.58 (2H, d,
J 9.2), 5.96 (1H, dt, J 15.6 and 5.2), 5.88 (1H, q, J 15.6 and 5.2), 5.40
(1H, d, J 3.2), 5.30 (1H, dd, J 10.4 and 5.6), 5.10 (1H, dd, J 10.4 and
3.2), 4.82 (1H, t, J 3.2), 4.01–4.18 (3H, m), 3.95 (2H, d, J 5.2), 1.93–
2.14 (12H, 4 Â s); 13C NMR (CDCl3): d 170.64, 170.17, 170.08,
169.77, 152.98, 138.32, 132.15, 126.36, 124.85, 111.39, 72.24,
68.45, 68.23, 67.95, 67.82, 61.73, 44.89, 20.73, 20.69, 20.64; HRMS:
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calcd for
531.1670.
C23H28N2O11Na (M+Na): m/z 531.1591; found: m/z
1.2.6. Data for 7c
IR (film) cm-1: 3398, 2926, 1748, 1622, 1532, 1351, 1228, 1050,
738; 1H NMR (CDCl3): d 7.55 (1H, d, J 7.6), 7.40 (1H, s), 7.32 (1H, t, J
8.4), 6.90 (1H, d, J 1.2), 5.99 (1H, dt, J 15.6 and 5.2), 5.92 (1H, q, J
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5.11 (1H, dd, J 10.4 and 3.2), 4.82 (1H, t, J 3.2), 4.02–4.15 (3H,
m), 3.93 (2H, d, J 5.2), 1.97–2.14 (12H, 4 Â s); 13C NMR (CDCl3) d:
170.61, 170.18, 170.07, 169.85, 149.44, 148.44, 132.92, 129.81,
124.40, 119.04, 112.38, 106.52, 72.39, 68.35, 68.25, 67.92, 61.73,
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