An unexpected rearrangement of pent-4-enofuranosides to cyclopentanones upon hydrogenolysis of the anomeric benzyl group

Article abstract of DOI:10.1016/j.carres.2016.06.006

During our synthesis toward the unique nucleoside antibiotic A201A, we were surprised to find that a benzyl arabino-pent-4-enofuranoside underwent a Ferrier II-like rearrangement readily to provide the corresponding cyclopentanone derivative in high yield and stereoselectivity upon hydrogenolysis of the anomeric benzyl group.

Full text of DOI:10.1016/j.carres.2016.06.006

Carbohydrate Research 432 (2016) 36e40
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Note
An unexpected rearrangement of pent-4-enofuranosides to
cyclopentanones upon hydrogenolysis of the anomeric benzyl group
Shenyou Nie, Xiaoping Chen, Yuyong Ma, Wei Li*, Biao Yu**
State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling
Road, Shanghai, 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
During our synthesis toward the unique nucleoside antibiotic A201A, we were surprised to find that a
benzyl arabino-pent-4-enofuranoside underwent a Ferrier II-like rearrangement readily to provide the
corresponding cyclopentanone derivative in high yield and stereoselectivity upon hydrogenolysis of the
anomeric benzyl group.
Received 17 May 2016
Received in revised form
13 June 2016
Accepted 16 June 2016
Available online 18 June 2016
© 2016 Elsevier Ltd. All rights reserved.
Keywords:
Cyclopentanone
Ferrier II rearrangement
Furanoside
Hydrogenolysis
Exocyclic enol ether
1. Introduction
converting pent-4-enofuranosides into the corresponding cyclo-
pentanones [16]. Thus, Gallos et al. reported a nitrile oxide-assisted
Polyoxygenated cyclopentanoids are the essential scaffolds of
many bioactive molecules of pharmaceutical interest, including
carbocyclic nucleosides [1], glycosidase inhibitors [2], prosta-
glandin [3,4], pentenomycin [5], and caryose [6,7]. Over the past
few decades, numerous approaches to the construction of the
cyclopentanoid skeleton have been developed [2,8e11]. A few of
these approaches employ carbohydrates as starting materials to
furnish polyoxygenated cyclopentanoids, however, in multiple
steps and unsatisfactory efficiency [12e15].
On the other hand, carbohydrates have been extensively used in
the construction of polyoxygenated cyclohexanoids [16e22], that
could be mainly attributed to the classical Ferrier II rearrangement
of hex-5-enopyranosides promoted by a stoichiometric or catalytic
amount of Lewis acids such as Hg(II) or Pd(II) salts (Scheme 1)
[17,23e28]. This rearrangement involves a cleavage of the acetal
rearrangement to prepare five-membered carbocycles in two steps,
involving a nitrile oxide cycloaddition and subsequent reductive
cleavage of the spiroisoxazoline intermediate to promote the key
aldol-like cyclization [14,15]. Other examples are limited only on
specific substrates, such as spiro dienones [36e38], vinyl alkyli-
denes [39,40], and g-enollactones [41]. Rearrangements of pyran-
osides to construct cyclopentanoids with zirconium, samarium and
palladium were also reported [42e47]. It is noteworthy that all the
resultant cyclopentanones in these Ferrier II-like reactions remain
redundant substituents, which are difficult to remove afterwards.
Very recently, during our synthesis toward a unique nucleoside
antibiotic A201A [48], we were surprised to find a cyclopentanone
product resulting from the rearrangement of
a
pent-4-
enofuranoside upon hydrogenolysis of the anomeric benzyl
group. Herein, we report this unexpected discovery and a brief
examination of the reaction scope.
bond and
a subsequent aldol-like intramolecular cyclization.
However, despite its reliable performance and widespread appli-
cation in synthesizing cyclohexanone derivatives [27,29e35], the
Ferrier II rearrangement has rarely been applied successfully in
2. Results and discussion
Disaccharide 1 bearing an arabino-pent-4-enofuranoside moi-
ety was envisioned as a key intermediate in our synthetic studies
* Corresponding author.
** Corresponding author.
toward nucleoside antibiotic A201A (Scheme 2) [48]. Thus,
D-
E-mail addresses: lmwave@mail.sioc.ac.cn (W. Li), byu@mail.sioc.ac.cn (B. Yu).
arabinose was converted into 5-aldehyde-furanoside 2 in 9 steps
http://dx.doi.org/10.1016/j.carres.2016.06.006
0008-6215/© 2016 Elsevier Ltd. All rights reserved.

S. Nie et al. / Carbohydrate Research 432 (2016) 36e40
37
Table 1
Attempts to deprotect the benzyl group and the unexpected rearrangement of
disaccharide 1.
Entry
Conditions
Results
1
2
3
4
LDBB, THF, ꢀ78 ꢁC.
Complex
Complex
No reaction
7, 90%
FeCl3, dry CH2Cl2, rt.
Pd/C, H2(1 atm), ethyl acetate, Et3N, rt.
Raney Ni, EtOH, rt.
Scheme 1. Ferrier II rearrangement.
Scheme 2. The preparation of disaccharide 1 toward the synthesis of A201A.
with an overall yield of 22% (see SI for detailed information)
[49e52]. Addition of aldehyde 2 with tris-(phenylthio)methyl-
lithium at ꢀ78 ꢁC resulted in an unstable phenylthioorthoester,
spectra (see SI for more details): The signal at 208 ppm in 13C NMR
spectrum revealed the generation of carbonyl group at C1; the
nascent 3-OH was confirmed by its active hydrogen signal at
2.61 ppm in 1H NMR spectrum; the configuration of C3 was pre-
which was treated with CuO and CuCl2 to give
a
-OH methyl ester 3
in good yield. Oxidation of the nascent
a
-OH on 3 and subsequent
sumed by the absence of NOE correlation between H3 (
d 4.03 ppm)
enolization in the presence of Cs2CO3 and Me2SO4 led to enol
methyl ester 4, which was then reduced with DIBAL-H to give
alcohol 5. Glycosyaltion of 5 with imidate 6 (prepared from
and H4 ( 4.21 ppm). Although the NMR spectra could not provide
d
enough information to determine the configuration of C2, the
rearrangement turned out to be highly stereoselective with only
trace epimers being observed.
Further study was then conducted on monosaccharide 4 bearing
a conjugated exocyclic enol ether which was much less reactive
(Scheme 3). As expected, the rearrangement was much slower
upon treatment of Raney Ni in EtOH, and most of 4 remained intact
D
-mannose according to the reported procedure) [48] promoted
with BF3$OEt2 at ꢀ45 ꢁC furnished the desired disaccharide 1 in 92%
yield.
To deprotect the anomeric benzyl group on 1 for further syn-
thetic transformations toward A201A, several debenzylation con-
ditions were examined, wherein the reactive exocyclic enol ether
moiety should remain intact. As depicted in Table 1, either Lewis
acid FeCl3 or radical reagent LiDBB (lithium di-tert-butylbiphenyl)
made disaccharide 1 fully decomposed and led to complex mix-
tures (entry 1, 2) [53,54]. On the other hand, no reaction was
observed in Pd/C-catalyzed hydrogenolysis in the presence of Et3N
(entry 3). Surprisingly, when disaccharide 1 was treated with a
catalytic amount of Raney Ni in EtOH at rt, cyclopentanone 7
resulting from a rearrangement was afforded in 90% yield. The
structure of cyclopentanone 7 was elaborated with a set of NMR
Scheme 3. Rearrangement of conjugated enol ether furanoside 4 under Pd/C-catalyzed
hydrogenolysis.

38
S. Nie et al. / Carbohydrate Research 432 (2016) 36e40
after 12 h at rt. A better conversion was obtained under the con-
ditions of Pd/C-catalyzed hydrogenolysis under H2 in ethyl acetate
at rt, leading to the desired cyclopentanone 8 in 39% yield and
recovered 4 in 40% yield.
chromatography was performed using silica gel 60 F254 glass
plates. Compound spots were visualized by UV light (254 nm) and
by heating with a solution with 10% H2SO4 in ethanol. Flash column
chromatography was performed on silica gel. NMR spectra were
referenced using Me4Si (0 ppm), residual CHCl3 (1H NMR
To briefly check the scope of this rearrangement, three benzyl
pent-4-enofuranosides 9e11 were prepared from either
D
-arabi-
d
d
d
¼ 7.26 ppm, 13C NMR
d
¼ 77.16 ppm), CD3OD (1H NMR
nose or -ribose (see SI for the preparation). These substrates were
D
¼ 3.30 ppm, 13C NMR
d
¼ 49.00 ppm), or D2O (1H NMR
then examined under the conditions of Raney Ni in EtOH at rt. As
depicted in Table 2, TIPS-protected arabino-enofuranoside 9, which
was similar to the furanosyl unit of disaccharide 1, could be con-
verted smoothly into the desired cyclopentanone 12 in 86% yield
and excellent stereoselectivity (entry 1). The mechanism was hy-
pothesized to involve the cleavage of C1eO5 bond and subsequent
attack of the resultant aldehyde by enol [18,19,41,55]. However,
replacing TIPS with Ac groups led to full hydrolysis of 10 under
these conditions (entry 2). This result implied that the bulkiness of
the TIPS groups are important for the rearrangement. However,
TIPS-protected ribo-enofuranoside 11 turned out to be stable upon
treatment of Raney Ni in EtOH even at 90 ꢁC. This outcome could be
attributed to the configuration of C2 being critical to the hydro-
genolysis of the anomeric benzyl group.
¼ 4.67 ppm). Peak and coupling constant assignments are based
on 1H NMR, 1He1H COSY, and 1He13C HMQC experiments. Splitting
patterns are indicated as s (singlet), d (doublet), t (triplet), q
(quartet), and brs (broad singlet) for 1H NMR data. ESI-MS and
MALDI-MS were run on an IonSpec Ultra instrument using
HP5989A or VG Quattro MS. Optical rotations were measured using
a Perkin-Elmer 241 polarimeter.
4.2. Methyl (benzyl 2,3-di-O-triisopropylsilyl-a-D-altrofuranosid)
uronate 3
To a solution of tris(phenylthio)methane (311 mg, 0.92 mmol) in
freshly distilled THF (3.5 mL) was added dropwise nBuLi (1.6 M in
hexanes, 0.54 mL, 1.26 mmol) at ꢀ78 ꢁC. The mixture was stirred at
that temperature for 2 h, and aldehyde 2 (419 mg, 0.74 mmol) in
THF (3.5 mL) was added dropwise over 10 min. The mixture was
stirred at that temperature for additional 3 h, and was then
quenched with saturated aqueous NH4Cl. The mixture was
extracted with CH2Cl2. The organic layer was dried over Na2SO4,
filtered, and concentrated in vacuo. The residue was instable and
thus was used in the next reaction without further purification.
To a solution of the residue above in CH2Cl2 (1.2 mL) and MeOH
(13.1 mL) were added CuO (86 mg, 1.1 mmol), CuCl2 (313 mg,
2.33 mmol) and H2O (1.2 mL) at rt. The resulting mixture was
stirred overnight, and was then filtered and washed with CH2Cl2.
The filtrates were concentrated in vacuo. The residue was diluted
with CH2Cl2 and water, and was then extracted with CH2Cl2. The
organic layer was washed with saturated aqueous NaHCO3 and
brine, dried over Na2SO4, filtered, and concentrated in vacuo. The
residue was purified by silica gel column chromatography (petro-
3. Conclusion
In conclusion, we have discovered a Ferrier II-like rearrange-
ment upon hydrogenolysis of the anomeric benzyl group on pent-
4-enofuranosides, however, with a different mechanism. Although
the highly efficient rearrangements are only observed herein on
arabinofuranoside substrates with bulky TIPS protecting groups, it
is, to the best of our knowledge, the first rearrangement of eno-
furanosides to cyclopentanones resulting from hydrogenolysis
conditions. Further studies on the scope of this reaction and its
application in the synthesis are still in progress.
4. Experimental
4.1. General methods
leum ether-EtOAc, 100:1 to 30:1 to 10:1) to afford 3 (361 mg, 78%)
28
as a colorless syrup: [
CDCl3)
a
]
D
¼ þ58.3 (c 0.7, CHCl3); 1H NMR (400 MHz,
All reactions were carried out under nitrogen or argon with
anhydrous solvents in flame-dried glassware, unless otherwise
noted. All glycosylation reactions were performed in the presence
of 4 Å or 5 Å molecular sieves, which were flame-dried immedi-
ately before use in the reaction under high vacuum. Glycosylation
solvents were dried using a solvent purification system and used
directly without further drying. The chemicals used were reagent
grade as supplied, except where noted. Analytical thin-layer
d
7.36e7.24 (m, 5H), 5.08 (s, 1H), 4.78 (d, J ¼ 12.1 Hz, 1H),
4.50 (d, J ¼ 12.1 Hz, 1H), 4.46e4.39 (m, 2H), 4.38 (s, 1H), 4.25 (s, 1H),
3.77 (s, 3H), 3.55 (d, J ¼ 5.7 Hz, 1H), 1.04 (s, 42H); 13C NMR
(100 MHz, CDCl3) d 172.8, 138.1, 128.3, 128.0, 127.5, 108.3, 89.7, 82.8,
79.0, 71.9, 69.0, 52.4, 18.1, 18.02, 17.97, 12.5, 12.4; HRMS (MALDI-
FTMS) calcd for
633.3609.
C
32H58O7Si2Na [MþNa]þ: 633.3613, found:
4.3. Methyl (benzyl (Z)-2,3-di-O-triisopropylsilyl-5-O-methyl-a-D-
altro-hex-4-enofuranosid)uronate 4
Table 2
Examination of the rearrangement of benzyl pent-4-enofuranosides 9e11.
To a solution of alcohol 3 (76 mg, 0.12 mmol) in DMSO (1.2 mL)
was added Ac2O (0.79 mL) at rt. The mixture was stirred at rt
overnight before it was quenched with MeOH. The mixture was
diluted with H2O, and extracted with EtOAc. The organic layer was
washed with brine, dried over Na2SO4, filtered, and concentrated in
vacuo. The residue was purified by silica gel column chromatog-
Entry
Substrates
Results
12, 86%
Hydrolysis
No reaction
raphy (petroleum ether-EtOAc, 12:1) to afford an
a-keto-ester
1
2
3
9
10
11
28
(69 mg, 91%) as a colorless syrup: [
NMR (400 MHz, CDCl3)
a
]
¼ þ56.8 (c 1.1, CHCl3); 1H
D
d
7.36e7.25 (m, 6H), 5.18 (s, 1H), 5.05 (s, 1H),
4.84 (d, J ¼ 12.0 Hz,1H), 4.60 (s,1H), 4.54 (d, J ¼ 12.0 Hz,1H), 4.20 (s,
1H), 3.85 (s, 3H), 1.10e0.98 (m, 42H); 13C NMR (125 MHz, CDCl3)
d
191.6, 162.9, 138.0, 128.2, 127.9, 127.5, 109.8, 90.5, 81.5, 80.3, 69.7,
52.7, 18.10, 18.08, 17.94, 17.87, 12.4, 12.2; HRMS (MALDI-FTMS) calcd
for C32H56O7Si2Na [MþNa]þ: 631.3457, found: 631.3476.
To a solution of the a-keto-ester above (53 mg, 0.08 mmol) in

S. Nie et al. / Carbohydrate Research 432 (2016) 36e40
39
MeCN (3.6 mL) were added Me2SO4 (0.077 mL, 0.81 mmol) and
Cs2CO3 (53 mg, 0.16 mmol) at rt. The mixture was stirred overnight,
and was then quenched with 1 M aqueous NaOH over 10 min. The
mixture was extracted with CH2Cl2. The organic layer was dried
over Na2SO4, filtered, and concentrated in vacuo. The residue was
purified by silica gel column chromatography (petroleum ether-
purified by silica gel column chromatography (petroleum ether-
EtOAc, 10:1) to afford 7 (8 mg, 90%) as a colorless syrup: 1H NMR
(400 MHz, CDCl3)
d
8.05 (d, J ¼ 7.4 Hz, 2H), 7.58 (t, J ¼ 7.4 Hz, 1H),
7.45 (t, J ¼ 7.7 Hz, 2H), 5.47 (s, 1H), 4.81 (s, 1H), 4.22e4.19 (m, 1H),
4.14 (d, J ¼ 7.5 Hz,1H), 4.04 (brs, 1H), 4.00 (d, J ¼ 9.8 Hz, 1H), 3.60 (d,
J ¼ 9.8 Hz, 1H), 3.58e3.54 (m, 1H), 3.53 (s, 3H), 3.47e3.44 (m, 4H),
3.39 (s, 3H), 3.15 (t, J ¼ 9.4 Hz, 1H), 2.61 (d, J ¼ 5.8 Hz, 1H), 1.35 (d,
J ¼ 6.2 Hz, 3H), 1.24e1.08 (m, 42H); 13C NMR (100 MHz, CDCl3)
EtOAc, 60:1 to 40:1) to afford 4 (36 mg, 67%) as colorless syrup:
26
[
d
a
]
¼ þ125.3 (c 0.73, CHCl3); 1H NMR (400 MHz, CDCl3)
D
7.43e7.22 (m, 5H), 5.32 (s, 2H), 4.87 (d, J ¼ 12.0 Hz, 1H), 4.65 (d,
d 208.1, 165.8, 133.4, 130.1, 130.0, 128.6, 98.3, 82.0, 81.6, 80.2, 79.7,
J ¼ 12.0 Hz, 1H), 4.27 (s, 1H), 3.77 (s, 3H), 3.64 (s, 3H), 1.15e0.93 (m,
78.6, 77.4, 74.7, 69.0, 68.5, 64.0, 60.8, 57.7, 53.1, 18.40, 18.36, 18.3,
18.2, 13.2, 13.0; HRMS (MALDI-FTMS) calcd for C40H70O11Si2Na
[MþNa]þ: 805.4349, found: 805.4362.
42H); 13C NMR (100 MHz, CDCl3)
d
165.2, 162.2, 137.3, 128.3, 128.2,
128.0, 127.8, 111.3, 80.0, 76.6, 71.0, 60.4, 51.7, 18.2, 18.0, 12.7, 12.4;
HRMS (MALDI-FTMS) calcd for C33H58O7Si2Na [MþNa]þ: 645.3613,
found: 645.3632.
4.7. (3S,4R,5S)-2-methoxycarbonyl-2-O-methyl-4,5-di-O-
triisopropylsilyl-3-hydroxy-cyclopentanone 8
4.4. Benzyl (Z)-2,3-di-O-triisopropylsilyl-5-O-methyl-a-D-altro-
hex-4-enofuranoside 5
To a solution of 4 (15 mg, 0.024 mmol) in EtOAc (3 mL) was
added 10% Pd/C (12 mg). The mixture was stirred overnight under
To a solution of ester 4 (67 mg, 0.11 mmol) in CH2Cl2 (1.2 mL)
was added DIBAL-H (0.4 mL, 0.4 mmol) at ꢀ40 ꢁC. Another portion
of DIBAL-H (0.4 mL, 0.4 mmol) was added after 30 min. The reaction
was quenched with saturated potassium sodium tartrate. The
mixture was extracted with CH2Cl2, dried over Na2SO4, and
concentrated in vacuo. The residue was purified by silica gel column
1
atm hydrogen atmosphere. The mixture was filtered and
concentrated in vacuo. The residue was purified by silica gel column
chromatography (petroleum ether-EtOAc, 30:1) to afford 8 (5 mg,
39%) as a syrup: 1H NMR (400 MHz, CDCl3)
d
4.38 (d, J ¼ 8.0 Hz, 1H),
4.16e4.09 (m, 2H), 3.80 (s, 3H), 3.60 (s, 3H), 2.72 (d, J ¼ 8.6 Hz, 1H),
1.22e1.07 (m, 42H); 13C NMR (100 MHz, CDCl3)
204.4, 168.5, 82.1,
d
chromatography (petroleum ether-EtOAc, 12:1) to afford 5 (58 mg,
81.6, 80.0, 77.4, 55.4, 52.9, 18.34, 18.28, 18.2, 13.2, 13.0; ESI-MS calcd
28
91%) as a colorless syrup: [
(400 MHz, CDCl3)
a]
¼ þ80.0 (c 0.9, CHCl3); 1H NMR
D
for C26H52O7Si2Na [MþNa]þ: 555.3, found: 555.7.
d
7.39e7.24 (m, 5H), 5.18 (s, 1H), 4.84 (d,
J ¼ 12.1 Hz, 1H), 4.63 (s, 1H), 4.59 (d, J ¼ 12.0 Hz, 1H), 4.25 (s, 1H),
4.8. (2S,3R,4S)-2,3-di-O-triisopropylsilyl-4-hydroxy-
cyclopentanone 12
4.20 (s, 2H), 3.75 (s, 3H), 1.06e1.00 (m, 42H); 13C NMR (100 MHz,
CDCl3) d 145.6, 137.7, 134.8, 128.3, 128.1, 127.7, 109.3, 80.6, 76.7, 70.1,
60.1, 58.7, 18.3, 18.2, 18.04, 17.99, 13.0, 12.4; HRMS (MALDI-FTMS)
To a solution of 9 (35 mg, 0.065 mmol) in EtOH (3 mL) and THF
(0.3 mL) was added Raney Ni (ca. 70 mg, wet). The mixture was
stirred at rt until the starting material was fully consumed as
indicated by TLC. The mixture was filtered and concentrated in
vacuo. The residue was purified by silica gel column chromatog-
calcd for C32H58O6Si2Na [MþNa]þ: 617.3664, found: 617.3665.
4.5. Benzyl (2-O-benzoyl-3,4-di-O-methyl-
a-D-rhamnopyranosyl)-
(1 / 6)-(Z)-2,3-di-O-triisopropylsilyl-5-O-methyl-a-D-altro-hex-4-
enofuranoside 1
raphy (petroleum ether-CH2Cl2, 2:1) to afford 12 (25 mg, 86%) as a
28
colorless syrup: [
a
]
¼ ꢀ27.0 (c 2.3, CHCl3); 1H NMR (400 MHz,
D
BF3$OEt2 (20 mL) was diluted with CH2Cl2 (2.26 mL) to give a
CDCl3)
d
4.29e4.24 (m, 1H), 4.16 (s, 1H), 3.82 (s, 1H), 3.19 (d,
0.07 M solution. To a solution of imidate 6 (31 mg, 0.071 mmol) and
alcohol 5 (14 mg, 0.024 mmol) in CH2Cl2 (2 mL) was added acti-
vated 4 Å MS (100 mg) under argon atmosphere. The mixture was
stirred at rt for 2 h, and then cooled to ꢀ45 ꢁC. BF3$OEt2 (0.1 mL,
0.07 M, 0.007 mmol) was added dropwise. The reaction was stirred
for 40 min, and then quenched with Et3N and filtered. The filtrate
was concentrated in vacuo. The residue was purified by silica gel
J ¼ 11.4 Hz, 1H), 2.70 (dd, J ¼ 19.5, 6.3 Hz, 1H), 2.45 (d, J ¼ 19.5 Hz,
1H), 1.25e1.04 (m, 42H); 13C NMR (100 MHz, CDCl3)
d
213.1, 78.4,
77.5, 75.3, 43.4, 18.04, 18.02, 17.97, 17.88, 12.3, 12.2; HRMS (ESI-
FTMS) calcd for
467.2990.
C
23H48O4Si2Na [MþNa]þ: 467.2983, found:
Acknowledgments
column chromatography (petroleum ether-EtOAc, 20:1) to afford 1
27
(19 mg, 92%) as a colorless syrup: [
NMR (400 MHz, CDCl3)
a
]
D
¼ þ74.7 (c 1.1, CHCl3); 1H
This work was supported by the National Natural Science
Foundation of China (21432012 and 21302210).
d
8.06 (d, J ¼ 7.3 Hz, 2H), 7.57 (t, J ¼ 7.4 Hz,
1H), 7.45 (t, J ¼ 7.6 Hz, 2H), 7.38e7.24 (m, 5H), 5.54 (d, J ¼ 1.8 Hz,
1H), 5.20 (s, 1H), 4.90 (s, 1H), 4.85 (d, J ¼ 12.0 Hz, 1H), 4.61e4.58 (m,
2H), 4.32 (d, J ¼ 11.9 Hz, 1H), 4.24 (s, 1H), 4.02 (d, J ¼ 11.9 Hz, 1H),
3.82e3.75 (m, 1H), 3.75 (s, 3H), 3.65 (dd, J ¼ 9.3, 3.2 Hz, 1H), 3.55 (s,
3H), 3.42 (s, 3H), 3.17 (t, J ¼ 9.4 Hz, 1H), 1.35 (d, J ¼ 6.2 Hz, 3H),
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carres.2016.06.006.
1.10e0.95 (m, 42H); 13C NMR (100 MHz, CDCl3)
d 165.8, 147.7, 137.7,
133.2, 132.4, 130.2, 130.0, 128.5, 128.3, 128.2, 127.7, 109.7, 97.8, 82.4,
80.6, 79.8, 76.4, 70.3, 69.2, 68.0, 65.5, 61.0, 59.1, 57.5, 18.3, 18.2, 18.1,
18.0, 13.0, 12.4; HRMS (MALDI-FTMS) calcd for C47H76O11Si2Na
[MþNa]þ: 895.4818, found: 895.4832.
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