A diversity oriented synthesis of D-erythro-sphingosine and siblings

Article abstract of DOI:10.1016/j.tetasy.2017.08.006

An efficient building block-based synthetic protocol has been developed for the synthesis of 3-ketosphingoids with various chain lengths using cross metathesis of a Garner's aldehyde-derived α,β-unsaturated ketone as the key step. Stereoselective reduction of the biomimetic precursors thus obtained provided D-erythro-sphingosine and truncated anaogues in good overall yields.

Full text of DOI:10.1016/j.tetasy.2017.08.006

Tetrahedron: Asymmetry xxx (2017) xxx–xxx
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
A diversity oriented synthesis of D-erythro-sphingosine and siblings
⇑
Amrita Ghosh, Shital K. Chattopadhyay
Department of Chemistry, University of Kalyani, Kalyani 741235, West Bengal, India
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient building block-based synthetic protocol has been developed for the synthesis of 3-ketosph-
Received 5 July 2017
Revised 26 July 2017
Accepted 7 August 2017
Available online xxxx
ingoids with various chain lengths using cross metathesis of a Garner’s aldehyde-derived a,b-unsaturated
ketone as the key step. Stereoselective reduction of the biomimetic precursors thus obtained provided D-
erythro-sphingosine and truncated anaogues in good overall yields.
Ó 2017 Elsevier Ltd. All rights reserved.
1
. Introduction
electron deficient alkenes as one of the partners in cross metathe-
sis reaction. Herein, we report a successful application of com-
pound 5 as a building block in cross-metathesis mediated
Sphingolipids of the general structure 1 (Fig. 1) are known to be
involved in nearly all aspects of cellular regulation and hence are
implicated in a myriad of disease related events including apopto-
sis, cell growth, cell differentiation and inflammation. Sphingosine
modular synthesis of N,O,O-triacetyl-D-erythro- sphingosine and
three chain truncated analogues.
1
2
, the basic structural core of the sphingolipids, is also important in
2
. Results and discussion
The unsaturated ketone 5 (Scheme 1) was prepared by oxida-
2
kinase regulation, cell signaling and in the studies of dermatitis.
For this and other reasons, sphingosines have received consider-
able attention from chemists and biologists over decades.
addition to the synthesis of the naturally occurring ones, design
and synthesis of analogues for biological understanding has
remained the major focus.5 In many of these synthetic studies,
the L-serine derived Garner’s aldehyde 3 has served as an impor-
tant starting material as metal-mediated stereoselective alkynyla-
tion or alkenylation of the latter has provided useful building
blocks, such as 4a–b for the synthesis of
and its analogues. Classical Wittig or sulfone-alkylation based
strategies for the installation of the pendant alkyl chain is now
being supplemented by metal-mediated coupling strategies. In
particular, the cross metathesis reaction of the suitably protected
3
,4
In
tion of the known allyl alcohol 7, obtained by non-selective vinyla-
tion of the L-serine derived Garner’s aldehyde 3. Previously, the
1
1
oxidation was carried out under Swern conditions at low temper-
ature. We have found that the oxidation could conveniently be car-
ried out at room temperature using IBX as oxidant with little
compromise in chemical yield or the stereochemical integrity.
Moreover, the unsaturated ketone 5 could be stored at 4 °C for
weeks with only a negligible loss of enantiomeric purity. With
access to a gram scale synthesis of 5, we next focused on its utility
along the projected line. After some initial explorations, it was
quickly realized that the cross metathesis of 5 with 1-pentadecene
proceeded rapidly (ꢀ1 h) when Grubbs’ 2nd generation catalyst
D-erythro-sphingosine
6
,7
8
9
allyl alcohol 4b has been thoroughly utilized for the synthesis of
the D-erythro-sphingoids, a minor limitation being the E/Z-selectiv-
(
(
1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro
phenyl-methylene)(trichlorohexylphosphne)ruthenium (Grubb-
ity and occasional dwindling of the chemical yield, mostly due to
use of two class-I type olefins in the cross-metathesis approaches.
On the other hand, the unsaturated ketone 5 has remained unex-
plored as cross metathesis partner for the synthesis of 3-keto-sph-
ingoids as bio-mimetic precursor10 of sphingosines. We opted to
use 5 as a type-II olefin in a cross metathesis reaction with the
expectation that some of the general problems associated with
cross metathesis of 4b may be avoided due to proven utility of
II) was used, as all attempts using Grubbs’ 1st generation catalysts
met with limited success. The cross metathesis product 6a was
obtained as a single isomer in good yield (91%) using only one
equivalent of the second olefin, thus obviating the need of an
excess of partner olefin as generally observed in similar situa-
1
2
tions. Stereoselective reduction of
a-aminoketones of type 6 to
the corresponding anti-amino alcohols is well documented and
various reagents have provided useful levels of selectivity in
1
3
4 3
demanding situtations. The NaBH /CeCl system has worked con-
sistently but under varied conditions with somewhat varying
stereoselectivity. We have found that the stereoselectivity in the
⇑
Corresponding author. Tel.: +91 33 25828750; fax: +91 33 25828282.
E-mail address: skchatto@yahoo.com (S.K. Chattopadhyay).
http://dx.doi.org/10.1016/j.tetasy.2017.08.006
957-4166/Ó 2017 Elsevier Ltd. All rights reserved.
0
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tetasy.2017.08.006

2
A. Ghosh, S. K. Chattopadhyay / Tetrahedron: Asymmetry xxx (2017) xxx–xxx
OH
O
Sphingosine derivatives with truncated alkyl chains have
recently been biologically evaluated with encouraging results.
X
Y
15
Carbohydrate
O
13 27
C H
HO
C
13
H
27
Thus, we opted to prepare sphingoids with C16, C15 and C13 chain
length to demonstrate the utility of 5 as a building block. Thus,
cross metathesis of 5 with shorter chain alkenes such as tridecene,
dodecene or decene proceeded with similar facility provided the
corresponding cross metathesis products 6b–d, respectively. Che-
lation-controlled reduction of each of these enones under the
developed conditions provided the corresponding anti-diols 8b–d
with good overall yield and stereoselectivity. In each of these
reductions, the corresponding syn-isomers were obtained as minor
products (8–14%) which could be separated. The diastereomeric
ratio for the reduction reaction in each case was as follows: 8a
HN
17 35
C H
NH2
2
a, X= H, Y = OH
Sphingolipid 1
2b, X= OH, Y = H
O
OPG
O
R
R
O
N
O
N
O
N
Boc
Boc
Boc
(
81:8), 8b (90:8), 8c (85:14), and 8d (88:11). The stereochemical
3
4
4
a, R = ethynyl
b, R = vinyl
5, R = H
, R= alkyl chain
assignment of the products 8b–d was based on the Felkin-Anh cyc-
lic transition state model with additional support from comparison
of available data for the two compounds further along the syn-
thetic sequence (vide experimental). Thus, each of the allylic alco-
hols 8b–d were subjected to deprotection of the oxazolidine ring
leading to the N-Boc-protected amino diols 9b–d and thence to fur-
ther deprotection-acetylation events leading to the triacetyl
derivatives 10b–d.
6
Figure 1. Sphingosines and building blocks for their synthesis.
O
O
OH
ii
i
O
O
O
R
N
N
N
Boc
Boc
Boc
3
. Conclusion
3
7
5
O
OH
In conclusion, we have demonstrated a short and efficient
iii
iv
diversity oriented biomimetic synthetic approach towards the syn-
thesis of the biologically important -erythro-sphingosine deriva-
tives involving 5 as a building block in good overall yields (40–
R
O
O
D
N
N
Boc
Boc
4
8%). The present methodology may be used to supplement exist-
6
6
6
6
a, R = C13H27, 91%
b, R = C11H23, 88%
8a, R = C13
8b, R = C11
8c, R = C10
8d, R = C
H
27, 81%
13b,f
14
ing methodologies
Further applications of this general strategy appear feasible. The
utility of 5 in this regard will be pursued in our laboratory.
for the preparation of 3-keto-sphingoids.
H
23, 90%
21, 85%
17, 88%
c, R = C10
H
21, 85%
H
d, R = C
8
H
17, 90%
8
H
4
4
. Experimental
OH
OAc
.1. General
v
vi
HO
R
OAc
R
NHBoc
NHAc
Column chromatography was performed on silica gel, Merck
grade 230–400 mesh and neutral alumina. Reactions were moni-
tored by thin-layer chromatography; TLC plates were visualized
with UV, in an iodine chamber, or with vanillin solution, unless
noted otherwise. Optical rotations were measured on a Rudolph
Autopol-IV polarimeter purchased from a DST grant. IR spectra
were recorded on a Perkin–Elmer Spectrum-1 instrument using
9
9
9
9
a, R = C13
H
27, 83%
10a, R = C13H27, 79%
10b, R = C11H23, 76%
10c, R = C10H21, 74%
b, R = C11
H
23, 72%
c, R = C10H21, 79%
d, R = C H17, 77%
10d, R = C H17, 69%
8
8
Scheme 1. Synthesis of N,O,O-triacetyl-
conditions: (i) vinylmagnesium bromide, THF, 0 °C, 1 h, 92%; (ii) IBX, DMSO, rt, 1 h,
5%; (iii) G-II (1 mol %), appropriate olefin, CH Cl , reflux, 1 h, 79–91%; (iv) NaBH
CeCl
, THF–MeOH, À15 °C, 2 h, 81–90%; (v) p-TSA, MeOH, 1 h, 77–83%; (vi) MeOH,
HCl (3 M), 50 °C, 3 h, 69–79%.
D-erythro-sphingoids 10a–d. Reagents and
1
13
KBr disks, chloroform solution or as neat. H NMR and C NMR
spectra were recorded on a Bruker Avance 400 MHz spectrometer,
operating at 400 and 100 MHz, respectively. Chemical shifts (d) are
8
2
2
4
,
3
1
given from TMS (0 ppm) as the internal standard for H NMR and
1
3
3
CDCl (77.0 ppm) for C NMR. The following abbreviations were
used to denote the multiplicities: s = singlet, d = doublet, t = triplet,
q = quartet, m = multiplet, dd = double doublet, ddd = doublet of
double doublet, dt = doublet of triplet, br = broad, etc. The data in
the parentheses indicate those for rotamers. Mass spectra were
recorded in Water Xevo-QTOF instrument purchased through a
DST-PURSE grant. THF, toluene, benzene and ether were freshly
distilled under argon from a purple solution of sodium benzophe-
none ketyl. Unless stated otherwise, all reagents were purchased
from commercial sources and used without additional purification.
reduction of 6a to 8a is influenced by the temperature as well as by
the solvent. The optimum result was obtained when a mixture of
THF and MeOH (1:5) was used as the solvent and the reduction
was conducted at À15 °C. The desired anti-product 8a was
obtained in 81% isolated yield together with the minor syn-isomer
(
8%), which could be separated. The deprotection of the oxazo-
lidine unit in the allyl alcohol 8a was smoothly achieved under
conventional conditions and the known Boc-protected aminodiol
9
a was obtained in good yield (83%). A one-pot deprotection of
4
.1.1. (4 R,S)-tert-Butyl 4-(1-hydroxyallyl)-2,2-dimethyloxazoli-
the Boc-group in the latter followed by exhaustive acetylation
resulted in the formation of 10a in an overall yield of 48% over four
steps from the building block 5. The spectroscopic and analytical
data of 10a were found to be in agreement with the known N,
O,O-triacetyl- -erythro-sphingosine.
dine-3-carboxylate 7
Vinyl magnesium bromide (1.0 M in THF, 4.4 ml, 4.4 mmol) was
added dropwise to a stirred solution of the Garner’s aldehyde 3
4
d
(
1 g, 4.4 mmol) in THF (8 mL) at 0 °C under nitrogen over 10 min
D
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A. Ghosh, S. K. Chattopadhyay / Tetrahedron: Asymmetry xxx (2017) xxx–xxx
3
and stirring was continued for an hour at the same temperature.
The reaction was quenched by the slow addition of saturated aque-
ous NH Cl solution (10 mL). The reaction mixture was diluted with
14.1. HRMS (QTOF): calcd for C26
obs. 460.3466.
H
47NNaO
4
(M+Na)+ 460.3403;
4
ethyl acetate (50 ml), and the combined organic extract was
4
.1.3.2. (S,E)-tert-Butyl 2,2-dimethyl-4-(tetradec-2-enoyl)oxazo-
lidine-3-carboxylate 6b. Colorless oil. Yield: 88%.
= À12.3 (c 0.1, CHCl ); IR (KBr):3010, 2924, 2853,
710 cm ; H NMR (400 MHz, CDCl ): d 6.94–6.88 (m, 1H), 6,24
washed with water (2 Â 25 mL) and brine (25 mL), and then dried
(
2 4
Na SO ). It was filtered and the filtrate was concentrated in vacuo.
[a
]
D
3
The residual mass was then purified by chromatography over silica
gel using a mixture of ethyl acetate/petroleum ether (3:7) as the
eluent to afford an epimeric mixture of the allyl alcohol 7
À1 1
1
3
(
1
d, J = 16.0 Hz, 1H), 4.44 (dd, J = 7.4, 3.6 Hz, 1H) (4.63–4.61, m,
H), 4.13–4.08 (m, 1H), 3.83 (dd, J = 8.0, 3.2 Hz, 1H) (3.88 (dd,
J = 9.2, 2.4 Hz, 1H), 2.14–2.19 (m, 2H), 1.64 (s, 3H) (1.58, s, 3H),
.42 (s, 3H) (1.48, s, 3H), 1.42–1.48 (m, 9H), 1.30 (br s, 9H), 1.18
(
2
1.04 mg, 92%) as a colourless viscous liquid. IR (KBr): 3408,
978, 2928, 1697 cm ; H NMR (400 MHz, CDCl ): d 5.79–5.75
3
À1
1
1
(
m, 1H), 5.31–5.25 (m, 1H), 5.17–5.12 (m, 1H), 4.26–4.08 (m,
H), 3.96–3.81 (m, 3H), 1.49 (d, J = 14 Hz, 3H), 1.41 (br s, 13H).
13
(
br s, 18H), 0.80 (t, J = 6.4 Hz, 3H). C NMR (100 MHz, CDCl
3
): d
2
1
96.5 (195.6), 149.5 (151.3), 125.2 (125.8), 94.9 (94.3), 80.3
1
3
C NMR (100 MHz, CDCl
117.8), 94.5, 81.1 (81.4) 74.1 (73.3), 64.7 (64.4), 61.9 (61.8),
8.3, 26.3 (27.1), 24.5 (24.2). HRMS (QTOF) calcd for C13 23NNaO
4
3
): d 154.2 (155.1), 136.7 (137.6), 116.2
(
80.6), 65.8 (65.4), 64.0 (63.8), 32.6, 31.9, 29.5, 29.4, 29.2 (29.3),
(
2
2
1
9.1, 28.2, 28.1 (28.2), 27.9 (27.8), 25.9, 25.1 (25.0), 24.1, 22.6,
4.0. HRMS (QTOF): calcd for C24 43NNaO
4
H
(M+Na)+ 432.3090;
H
+
(
M+Na) 280.1525; obs 280.1510.
obs. 432.3101.
4
.1.2. (S)-tert-Butyl 4-acryloyl-2,2-dimethyloxazolidine-3-carb-
4
.1.3.3. (S,E)-tert-Butyl 2,2-dimethyl-4-(tridec-2-enoyl)oxazo-
lidine-3-carboxylate 6c. Colorless oil (85%). [
= À36.0 (c
.05, CHCl ); IR (KBr): 2927, 2856, 1710 cm
400 MHz, CDCl ): d 6.87–6.94 (m, 1H), 6,23 (d, J = 16.0 Hz, 1H),
.44 (dd, J = 8.0, 3.2 Hz, 1H) (4.63–4.61, m, 1H), 4.09 (dd, J = 16.0,
oxylate 5
At first, IBX (446 mg, 1.56 mmol) was added in portions to a
stirred solution of alcohol 7 (200 mg, 0.77 mmol) in DMSO (5 mL)
and the resulting reaction mixture was stirred at room tempera-
ture for one hour. It was then quenched with saturated aqueous
a]
D
;
À1
1
0
(
3
H NMR
3
4
8
1
1
.8 Hz, 1H), 3.82 (dd, J = 9.2, 3.6 Hz, 1H) (3.88, J = 8.8, 2.4 Hz, dd),
.63 (s, 3H) (1.57 s, 3H), 1.42 (s, 3H) (1.47, s, 3H), 1.29 (br s, 9H),
.29 (br s, 7H), 1.19 (br s, 16H), 0.80 (t, J = 6.8 Hz, 3H): 13C NMR
4
NH Cl solution (10 mL) and filtered. The filtrate was diluted with
ethyl acetate (25 mL) and the combined organic extract was
washed with water (2 Â 25 mL) and brine (20 mL), and then dried
(
100 MHz, CDCl
3
): d 196.5 (195.7), 149.6 (151.3), 125.2 (125.8),
(
4
MgSO ). It was then filtered and the filtrate was concentrated in
9
4.9 (94.3), 80.3 (80.6), 65.8 (65.4), 64.0 (63.8), 32.6, 31.8, 29.4
vacuo to give a pale yellow liquid, which was purified by chro-
matography over silica gel using ethyl acetate/petroleum ether
(
29.5), 29.2 (29.3), 28.1 (28.3), 28.0, 27.9 (27.8), 26.0, 25.1 (25.0),
2
4
4.0, 22.6, 14.1. HRMS (QTOF): calcd for C23
18.2933. obs 418.2943.
H41NNaO
4
(M+Na)+
(
8
2:8) as the eluent to afford the unsaturated ketone 5 (170 mg,
5%) as a colourless viscous liquid. 0.5 [EA/PE (2:8)];
= À58.5 (c 0.4, CHCl = +54.1 (c 1.21, CHCl )};
, {Lit.11 ent. 5 [
IR (KBr): 2979, 2936, 1702 cm H NMR (400 MHz, CDCl ): d
f
R :
[
a
]
D
3
a
]
D
3
À1
1
;
3
4
.1.3.4. (S,E)-tert-Butyl 2,2-dimethyl-4-(undec-2-enoyl)oxazo-
6d. Colorless oil. Yield: 90%.
= À47.6 (c 0.1, CHCl ). IR (KBr): 2928, 2856, 1710 cm
NMR (400 MHz, CDCl ): d 6.87–6.94 (m, 1H), 6.23 (d, J = 16.0 Hz,
H), 4.44 (dd, J = 7.2, 3.6 Hz, 1H) (4.63–4.61, m, 1H), 4.10 (dd,
J = 17.0, 9.2 Hz, 1H), 3.83 (dd, J = 7.0, 3.6 Hz, 1H), 3.88 (dd, J = 9.2,
6
4
.44–6.56 (m, 1H): 6.25–6.35 (m, 1H), 5.79 (d, J = 10.4 Hz, 1H),
.50 (dd, J = 3.6, 7.4 Hz, 1H), [4.69–4.67 (m, 1H)], 4.11 (dd,
lidine-3-carboxylate
À1
1
[a
]
D
3
. H
J = 10.8, 18.2 Hz, 1H), 3.85 (dd, J = 3.6, 9.2 Hz, 1H) [3.90 (dd, 1H,
J = 9.0, 2.8)], 1.63 (s, 3H) [1.58 (s, 3H)], 1.42 (s, 3H) [1.45 (s, 3H)],
3
1
1
3
1
.30 (br s, 9H). C NMR (100 MHz, CDCl
3
): d 196.3 (195.6),
1
50.8, 129.4 (131.2), 94.7 (94.0), 80.1 (80.4), 65.1 (64.7), 63.4
2
3
0
.4 Hz, 1H), 2.16 (td, J = 14.5, 7.2 Hz, 2H), 1.63 (s, 3H) (1.58, s,
H), 1.42 (s, 3H) (1.48, s, 3H), 1.30 (br s, 9H), 1.19(br s, 12H),
.81 (t, J = 7.2 Hz, 3H).
(
63.1), 27.7 (27.8), 25.5, 24.7 (24.5), 23.6. HRMS (QTOF): calcd for
+
C
4
1
13
H
21NNaO
4
(M+Na) 278.1368; obs.278.1361.
13
3
C NMR (100 MHz, CDCl ): d, 196.6
(
(
(
195.7), 149.7 (151.3), 125.2 (125.8), 95.0 (94.4), 80.4 (80.8), 65.8
65.5), 64.0 (63.8), 32.7, 31.8, 29.3 (29.6), 29.2, 28.3, 28.2, 27.9
27.8), 25.2 (25.1), 24.1, 22.6, 14.0. HRMS (QTOF): calcd for C21
(M+Na)+ 390.2620; obs 390.2632.
.1.3. General procedure for cross metathesis
A solution of the unsaturated ketone 5 (220 mg, 0.863 mmol),
-pentadecene (0.2 mL, 0.863 mmol) in anhydrous and degassed
37
H -
NNaO
4
dichloromethane (3 mL) was treated with Grubbs’ II catalyst
7 mg, 1 mol %) and the reaction mixture was heated at reflux for
h under argon. It was then allowed to return to rt and then con-
(
1
4
.1.4. General procedure for anti-selective reduction of the
ketones
At first, CeCl
centrated in vacuo. The residual brownish mass was chro-
matographed over silica gel using a mixture of ethyl acetate and
petroleum ether (1:9) as eluent to provide the corresponding cross
metathesis product 6a (307 mg, 91%) as a viscous, colorless oil.
3
(221 mg, 0.59 mmol) was added in portions to a
stirred solution of compound 6a (260 mg, 0.59 mmol) in THF-
methanol (1:5, 5 mL) at À15 °C under nitrogen and stirred for
1
4
0 min. Next, NaBH (21 mg, 0.59 mmol) was added portion wise
over 5 min and stirring was continued for 2 h. It was then
4
.1.3.1. (S,E)-tert-Butyl 4-(hexadec-2-enoyl)-2,2-dimethyloxazo-
1
3b
quenched with saturated NH Cl solution (5 mL) and stirred at
lidine-3-carboxylate 6a.
[
a]
D
= À30.4 (c 0.15, CHCl
)]; IR (KBr): 2926, 2854, 1711,
701 cm ; H NMR (400 MHz, CDCl ): d 6.86–6.94 (m, 1H), 6.23
d, J = 15.6 Hz, 1H), 4.44 (dd, J = 8.0, 4.0 Hz, 1H), (4.62, dd, J = 7.2,
3
) [Lit.
4
room temperature for 15 min. The solvent was concentrated under
reduced pressure and the resulting suspension was diluted with
ethyl acetate (50 ml). It was then washed with water (20 mL), brine
[
1
(
a
]
D
= À30.0 (c 0.85 CHCl
3
À1
1
3
(
4
20 mL), dried (MgSO ) and then filtered. The filtrate was concen-
2
1
1
9
.8 Hz, 1H), 4.09 (dd, J = 17.0, 9.0 Hz, 1H), 3.84 (dd, J = 9.0, 4.0 Hz,
H), (3.89, dd, J = 9.0, 2.8 Hz, 1H), 2.16 (td, J = 14.8, 7.5 Hz, 2H),
.63 (s, 3H) (1.58, s, 3H), 1.42 (s, 3H), (1.48, s, 3H), 1.30 (br s,
trated in vacuo to leave a residual mass, which was purified
through chromatography over silica gel using a mixture of ethyl
acetate and petroleum ether (2:8) as the eluent to afford com-
pound 8a (211 mg, 81%) as a colourless viscous liquid. The corre-
sponding syn-isomer (23 mg, 8%) eluted later which was slightly
contaminated with the anti-isomer.
H), 1.19 (br s, 22H), 0.80 (t, J = 6.8 Hz, 3H). 1 C NMR (100 MHz,
3
3
CDCl ): d 196.7 (195.8), 149.7 (151.4), 125.2 (125.8), 95.1 (94.4),
8
2
0.5 (80.7), 65.9 (65.4), 64.1 (63.8), 32.7, 31.9, 29.6, 29.5, 29.4,
9.3, 29.2, 28.3, 28.2, 28.0, 27.9, 26.1 (25.2), 25.1 (24.1), 22.7,
Please cite this article in press as: Ghosh, A. ; Chattopadhyay, S. K. Tetrahedron: Asymmetry (2017), http://dx.doi.org/10.1016/j.
tetasy.2017.08.006

4
A. Ghosh, S. K. Chattopadhyay / Tetrahedron: Asymmetry xxx (2017) xxx–xxx
4
.1.4.1. (S)-tert-Butyl 4-((R,E)-1-hydroxyhexadec-2-en-1-yl)-2,2-
= À25.4 (c 0.5,
NMR (100 MHz, CDCl3) d 156.3, 134.1, 128.9, 79.8, 74.5, 62.5,
55.4, 32.3, 31.9, 29.7, 29.6, 29.5, 29.3, 29.2, 29.1, 28.4, 22.7, 14.1.
dimethyloxazolidine-3-carboxylate 8a.
CHCl ). IR (KBr): 3427, 2924, 2853, 1701 cm
400 MHz, CDCl ): d 5.70–5.63 (m, 1H), 5.36 (dd, J = 15.2, 4.8 Hz,
[a]
D
À1
1
+
3
;
H
NMR
HRMS (QTOF) calcd for C23
422.3201.
4
H45NNaO (M+Na) 422.3246; obs.
(
3
1
1
0
1
2
H), 4.14–4.05 (m, 2H), 3.97–3.94 (m, 1H), 3.78–3.75 (m, 1H),
.96 (td, J = 7.2, 4.0 Hz, 2H), 1.41 (br s, 15H), 1.18 (br s, 22H),
4.1.5.2. tert-Butyl ((2S,3R,E)-1,3-dihydroxyhexadec-4-en-2-yl)-
1
3
15f
.81 (t, J = 6.0 Hz, 3H). C NMR (100 MHz, CDCl
3
): d 154.2, 133.4,
carbamate 9b
(KBr): 3418, 2924, 2853, 1692 cm
.
Yield: 72%. [
a
;
]
D
1
= À7.1 (c 0.45, CHCl
3
); IR
):
À1
28.1, 94.3, 81.1, 74.1, 64.9, 62.3, 32.4 (32.3), 31.9, 29.7, 29.6,
H NMR (400 MHz, CDCl
3
9.5, 29.3, 29.2, 29.1, 29.0, 28.3, 26.2, 24.6, 22.7, 14.1. HRMS
d 5.71–5.66 (m, 1H), 5.44 (dd, J = 16, 6.8 Hz, 1H), 5.30(d,
J = 8.4 Hz, 1H), 4.22 (br s, 1H), 3.84 (dd, J = 11, 2.8 Hz, 1H), 3.69–
+
(
QTOF): calcd for C26
H
49NNaO
4
(M+Na) 462.3559; obs. 462.3656.
3
.52 (m, 2H), 3.09 (br s, 2H), 2.00–1.95 (m, 2H), 1.37 (br s, 9H),
1
3
4
.1.4.2. (S)-tert-Butyl 4-((R,E)-1-hydroxytetradec-2-en-1-yl)-2,2-
Yield: 90%. R : 0.5
). IR (KBr): 3432, 2925,
H NMR (400 MHz, CDCl ): d 5.67–5.64 (m,
H), 5.37 (dd, 1H, J = 14.5, 5.2 Hz), 4.13–4.05 (m, 2H), 3.94–3.77
3
1.18 (br s, 18H), 0.80 (t, J = 6.4 Hz, 3H). C NMR (100 MHz, CDCl ):
dimethyloxazolidine-3-carboxylate 8b.
EA/PE::3:7). [
f
d 156.2, 134.2, 128.8, 79.8, 74.6, 64.1, 62.6, 55.4, 32.3, 31.9, 29.7,
(
a
]
D
= À19.5 (c 0.2, CHCl
3
29.6, 29.5, 29.3, 29.2, 29.1, 28.4, 22.7, 14.1. HRMS (QTOF): calcd
À1
1
+
2
1
854, 1699 cm
.
3
for C21
H
41NNaO
4
(M+Na) 394.2933; obs. 394.2901.
(
(
1
2
m, 2H), 1.99–194 (m, 2H), 1.41 (br s, 15H), 1.18 (br s, 18H), 0.80
4.1.5.3. tert-Butyl ((2S,3R,E)-1,3-dihydroxypentadec-4-en-2-yl)-
1
3
t, J = 6.4 Hz, 3H). C NMR (100 MHz, CDCl
3
): d 154.8, 133.3,
28.1, 94.3, 80.9, 74.0, 64.9, 62.3, 32.4 (32.3), 31.9, 29.7 (29.6),
9.5, 29.4, 29.3, 29.2, 29.1, 29.0 (28.9), 28.3, 26.2, 22.7, 14.1. HRMS
carbamate 9c.
Yield: 79%.
[
a
]
D
= À4.5 (c 0.45, CHCl
= À4.1 (c 1.48, CH Cl )}. IR
): d
5.74–5.67 (m, 1H), 5.45 (dd, J = 16, 6.4 Hz, 1H), 5.26–5.25 (br s,
H), 4.25–4.24 (br s, 1H), 3.86 (dd, J = 11.2, 3.6 Hz, 1H), 3.72–3.53
3
);
5e
[a]
D
= À4.0 (c 1.1, CH
2
Cl
2
) {Lit.1
[
a
]
D
2
2
À1
1
(KBr): 3386, 2925, 2854, 1690 cm . H NMR (400 MHz, CDCl
3
+
(
QTOF): calcd for C24
4
H45NNaO (M+Na) 434.3246; obs. 434.3246.
1
4
.1.4.3. (S)-tert-Butyl 4-((R,E)-1-hydroxytridec-2-en-1-yl)-2,2-
(m, 2H), 2.82–2.72 (br s, 2H), 1.98 (q, J = 7.2 Hz, 2H), 1.38 (br s,
9H), 1.19 (br s, 16H), 0.81 (t, J = 7.2 Hz, 3H). C NMR (100 MHz,
15d
13
dimethyloxazolidine-3-carboxylate
8c
.
Yield:
85%.
[
1
(
3
(
1
2
a
]
D
= À42.0 (c 0.1, CHCl
3
). IR (KBr): 3417, 2925, 2854,
701 cm . H NMR (400 MHz, CDCl ): d 5.68–5.64 (m, 1H), 5.37
dd, J = 16.0, 5.6 Hz, 1H), 4.12–4.06 (m, 2H), 3.95 (br s, 1H), 3.87–
.77 (m, 1H), 1.96 (td, J = 8.0, 6.8 Hz, 2H), 1.41 (br s, 15H), 1.18
CDCl
3
): d 156.8, 134.2, 128.8, 79.8, 74.8, 62.6, 55.4, 32.3, 31.9,
À1
1
3
29.6, 29.5, 29.3, 29.2, 29.1, 28.3, 22.7, 14.1. HRMS (QTOF): calcd
for C20
+
4
H39NNaO (M+Na) 380.2777; obs. 380.2802.
1
3
br s, 16H), 0.81 (t, J = 6.8 Hz, 3H). C NMR (100 MHz, CDCl
3
): d
33.4, 128.1, 94.4, 81.0, 74.0, 64.9, 62.3, 32.4, 32.3, 31.9, 29.6,
9.5, 29.3, 29.2, 29.1 (29.0), 28.4 (26.2), 24.6, 22.7, 14.1. HRMS
4.1.5.4. tert-Butyl ((2R,3R,E)-1,3-dihydroxytridec-4-en-2-yl)car-
bamate 9d.
3439, 2925, 2854, 1701 cm . H NMR (400 MHz, CDCl
Yield: 77%. [
a
]
D
= À2.0 (c 0.2, CHCl
3
). IR (KBr):
): d 5.66–
À1
1
3
+
(
QTOF): calcd for C23
H43NNaO
4
(M+Na) 420.3090; obs. 420.3131.
5.73 (m, 1H), 5.45 (dd, J = 14.8, 6.4 Hz, 1H), 5.31 (d, J = 8.0 Hz,
H), 4.22–4.23 (br s, 1H), 3.85 (dd, J = 7.6, 3.2 Hz, 1H), 3.54–3.69
(m, 2H), 3.13 (br s, 2H), 1.95–1.99 (m, 2H), 1.38 (br s, 9H), 1.19
1
4
.1.4.4. (S)-tert-Butyl 4-((R,E)-1-hydroxyundec-2-en-1-yl)-2,2-
8d. Yield: 88%.
). IR (KBr): 3441, 2925, 2854,
701 cm . H NMR (400 MHz, CDCl ): d 5.68–5.62 (m, 1H), 5.37
dd, J = 15.4, 5.6 Hz, 1H), 4.12–4.05 (m, 2H), 4.00–3.95 (m, 1H),
1
3
dimethyloxazolidine-3-carboxylate
= À19.6 (c, 0.25, CHCl
3
(br s, 11H), 0.80 (t, J = 6.4 Hz, 3H). C NMR (100 MHz, CDCl ): d
156.3, 134.1, 128.9, 79.8, 74.6, 64.1, 62.5, 54.4, 32.3, 31.8, 29.7,
29.4, 29.3, 29.2, 29.1, 28.4, 22.6, 14.1. HRMS (QTOF): calcd for
[a
]
D
3
À1
1
1
(
3
+
18
C H35NO
4
(M) 329.2566; obs. 329.2604.
3
1
.82–3.77 (m, 1H), 1.96 (dt, J = 8.0, 6.8 Hz, 2H), 1.42–1.41 (m,
5H), 1.19 (br s, 12H), 0.81 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz,
4.1.6. General procedure for the preparation of triacetate
derivative
CDCl
3
): d 154.2, 132.4, 128.1, 94.4, 81.0, 74.0, 64.9 (64.2), 62.3,
2.4 (32.3), 31.9, 29.6 (29.7), 29.4 (29.3), 29.2 (29.1), 28.9 (28.3),
39
6.2 (27.1), 24.6 (24.3), 22.7, 14.1. HRMS (QTOF): calcd for C21H -
3
2
A solution of diol 9a (25 mg, 0.06 mmol) in a mixture of MeOH
(5 mL) and 3 (M) HCl (5 mL) was heated at 50 °C for 3 h. The
resulting solution was allowed to return to rt and then concen-
trated under reduced pressure to afford the hydrochloride salt
of the corresponding amino alcohol as a foam. The crude residue
was dissolved in dry pyridine (5 mL), and a catalytic amount of
DMAP and acetic anhydride (0.1 mL) were added to it. The reac-
tion mixture was allowed to stir at room temperature for 12 h.
It was then diluted with ethyl acetate (25 mL), washed with
HCl (1 M, 2 Â 20 mL), water (20 mL), brine (25 mL), and then
+
4
NNaO (M+Na) 392.2777; obs. 392.2791.
4
.1.5. General procedure for the deprotection of the oxazolidine
ring
A solution of alcohol 8a (40 mg, 0.09 mmol) in MeOH (2 mL)
was added dropwise to a magnetically stirred suspension of p-
toluenesulfonic acid (2 mg) in MeOH (2 mL) at room temperature.
The reaction mixture was stirred for 1 h and then quenched with
saturated NaHCO
20 mL) and extracted with CH
organic layer was dried (MgSO ), filtered, and the filtrate was con-
3
solution (2 mL). It was then diluted with water
4
dried (MgSO ). It was then filtered and the filtrate was evapo-
(
2
Cl
2
(2 Â 25 mL). The combined
rated in vacuo to afford a residue, which was purified by chro-
matography over silica gel using a mixture (1:1) of ethyl
acetate and petroleum ether to obtain compound 10a (21 mg,
79%) as a colourless solid.
4
centrated. The residual mass was purified by chromatography over
silica gel using a mixture (1:1) of EA/PE to give diol 9a (33 mg, 83%)
as a colorless viscous liquid.
4
10a.
CHCl
.1.6.1. (2S,3R,E)-2-Acetamidooctadec-4-ene-1,3-diyl diacetate
4
d
4
.1.5.1. tert-Butyl ((2S,3R,E)-1,3-dihydroxyoctadec-4-en-2-yl)-
[
a
]
D
= À13.2 (c 1.2, CHCl
). IR (KBr): 2921, 2850, 1736, 1692 cm
): d 5.67–5.75 (m, 2 H); 5.32 (dd, J = 14.8, 7.6 Hz,
3
), Lit.
[
a
]
D
= À12.0 (c 1.0,
9
d
À1 1
carbamate 9a.
R
f
:
[
a
]
D
= À6.0 (c 0.35, CHCl
)]; IR (KBr) max 3343, 2920, 2850,
H NMR (400 MHz, CDCl ) d 5.69 (dt, 1H, J = 15.6,
3
)
[
Lit.
3
.
H NMR
[a
]
D
= À2.3 (c 0.88, CHCl
3
m
(400 MHz, CDCl
3
À1
1
1
7
+
3
6
689 cm
;
3
1H), 5.21 (t, J = 7.2 Hz, 1H), 4,33–4.39 (m, 1H), 4.22 (dd, J = 9.8,
6.0 Hz, 1H), 3.97 (dd, J = 11.0, 4.0 Hz, 1H), 2.00 (s, 3H) 1.99 (s,
.2 Hz), 5.44 (dd, 1H, J = 15.4, 6.8 Hz), 5.30 (d, 1H, J = 8.4 Hz), 4.21
(br s, 1H), 3.84 (dd, 1H, J = 11.2, 3.8 Hz), 3.61 (dd, 2H, J = 7.8,
.2 Hz), 3.52 (br s, 1H), 3.19 (br s, 1H), 1.97 (td, 2H, J = 7.2,
3H), 1.91 (s, 3H), 1.18–1.27 (br s, 24H), 0.81 (t, J = 6.8 Hz, 3H). 13
C
3
NMR (100 MHz, CDCl ): d 171.0, 170.0, 169.8, 137.5, 124.1, 73.9,
1
3
.8 Hz) 1.37 (br s, 9H), 1.19 (br s, 22H), 0.80 (t, 3H J = 6.8 Hz):
C
62.6, 50.6, 32.3, 31.9, 29.7, 29.6, 29.5, 29.4, 29.2, 28.9, 23.3, 22.7,
Please cite this article in press as: Ghosh, A. ; Chattopadhyay, S. K. Tetrahedron: Asymmetry (2017), http://dx.doi.org/10.1016/j.
tetasy.2017.08.006

A. Ghosh, S. K. Chattopadhyay / Tetrahedron: Asymmetry xxx (2017) xxx–xxx
5
2
4
1.1, 20.8, 14.1. HRMS (QTOF): calcd for C24
48.3039; obs 448.3002.
H
43NNaO
5
(M+Na)+
7223; (d) Abraham, E.; Davies, S. G.; Millican, N. L.; Nicholson, R. L.; Roberts, P.
M.; Smith, A. D. Org. Biomol. Chem. 2008, 6, 1655; (e) Wisse, P.; Gold, H.;
Mirzaian, M.; Ferraz, M. J.; Lutteke, G.; van der Berg, R. J. B. H. N.; van den Elst,
H.; Lugtenburg, J.; van der Marel, G. A.; Aerts, J. M. F. G.; Code, J. D. C.;
Overkleeft, H. Eur. J. Org. Chem. 2015, 2661; (f) Kumar, P.; Dubey, A.; Puranik, V.
G. Org. Biomol. Chem. 2010, 8, 5074; Morales-Serna, J. A.; Sauza, A.; Padrón de
Jesús, G.; Gaviño, R.; García de la Mora, G.; Cárdenas, J. Tetrahedron Lett. 2013,
4
.1.6.2. (2S,3R,E)-2-Acetamidohexadec-4-ene-1,3-diyl diacetate
0b. Colourless solid. Yield: 76%. [ ),
= À12.3 (c 0.3). IR (KBr): 2920, 2850, 1736, 1655 cm
): d 5.75–5.68 (m, 2H), 5.32 (dd, J = 14.0,
.4 Hz, 1H), 5.21 (t, J = 6.0 Hz, 1H), 4,38–4.33 (m, 1H), 4.22 (dd,
J = 10.2, 6.0 Hz, 1H), 3.97 (dd, J = 11.6, 4.0 Hz, 1H), 2.00 (s, 3H),
1
Lit.
a
]
D
= À12.7 (c 1.2, CHCl
3
1
5g
À1
[a]
D
.
5
4, 7111; (m) Ndonye, R. M.; Izmirian, D. P.; Dunn, M. F.; Yu, K. O. A.; Porcelli, S.
1
H NMR (400 MHz, CDCl
3
A.; Khurana, A.; Kronenberg, M.; Richardson, S. K.; Howell, A. R. J. J. Chem. Soc.,
Perkin Trans. 1997, 1, 2389.
(a) Liew, S. K.; Kaldas, S. J.; Yudin, A. K. Org. Lett. 2016, 18, 6268–6271; (b)
Alcaide, A.; Llebaria, A. J. Org. Chem. 2014, 79, 2993; (c) Das, P.; Kundooru, S.;
Shaw, A. K. RSC Adv. 2016, 6, 14505; (d) Siciliano, C.; Barattucci, A.; Bonaccorsi,
P.; Di Gioia, M. L.; Leggio, A.; Minuti, L.; Romio, E.; Temperini, A. J. Org. Chem.
6
5
.
1
.99 (s, 3H), 1.91 (s, 3H), 1.18 (br s, 20H), 0.81 (t, J = 6.8 Hz, 3H).
C NMR (100 MHz, CDCl ): d 171.0, 170.1, 169.7, 137.4, 124.1,
3
3.8, 62.5, 50.6, 32.2, 31.9, 29.6, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1,
1
3
2014, 79, 5320; (d) Devi, T. J.; Saikia, B.; Barua, N. C. Tetrahedron 2013, 69, 3817;
7
2
C
(
e) Rives, A.; Baudoin-Dehoux, C.; Nathalie Saffon, N.; Nathalie Andrieu-
8.9, 23.3, 23.2, 22.6, 21.1, 20.8, 14.1. HRMS (QTOF): calcd for
Abadiec, N.; Genisson, Y. Org. Biomol. Chem. 2011, 9, 8163; (f) Moreno, M.;
Caterina Murruzzu, C.; Riera, A. Org. Lett. 2011, 13, 5184–5187; (g) Saikia, P. P.;
Goswami, A.; Baishya, G.; Barua, N. C. Tetrahedron Lett. 2009, 50, 1328; (h)
Grijalvo, S.; Matabosch, X.; Llebaria, A.; Delgado, A. Eur J. Org. Chem. 2008, 150;
(i) Chandrasekhar, S.; Saritha, B.; Jagadeshwar, V.; Prakash, S. J. Tetrahedron:
Asymmetry 2006, 17, 1380.
+
22
H
39NNaO
5
(M+Na) 420.2726; obs 420.2734.
4
1
CHCl
(
.1.6.3. (2S,3R,E)-2-Acetamidopentadec-4-ene-1,3-diyl diacetate
0c. Colourless solid. Yield: 74% yield. [
= À21.0 (c 0.2,
). IR (KBr): 2922, 2851, 1736, 1655 cm
400 MHz, CDCl ): d 5.74–5.69 (m, 1H), 5.62 (d, J = 9.2 Hz, 1H),
.32 (dd, J = 12.0, 7.2 Hz, 1H), 5.21 (t, J = 7.2 Hz, 1H), 4,38–4.33
a]
D
À1
1
6. (a) Garner, P.; Park, J. M. J. Org. Chem. 1983, 48, 4155; (b) Harold, P. Helv. Chim.
Acta 1988, 71, 354; (c) McKillop, A.; Taylor, R. J. K.; Watson, R.; Lewis, N.
Synthesis 1994, 31; (d) Campbell, A. D.; Raynham, T. M.; Taylor, R. J. K. Synthesis
1998, 1707.
3
.
H NMR
3
5
7.
For some reviews, see; (a) Liang, X.; Andersch, J.; Bols, M. J. Chem. Soc., Perkin
Trans. 1 2001, 2136; (b) Bera, S.; Mondal, D.; Singh, M.; Kale, R. K. Tetrahedron
(
1
m, 1H), 4.24 (dd, J = 11.6, 6.4 Hz, 1H), 3.96 (dd, J = 11.4, 4.0 Hz,
H), 2.00 (s, 3H), 1.99 (s, 3H), 1.91 (s, 3H), 1.18 (br s, 18H), 0.80
2
013, 69, 969.
8. For an example, see: Murakami, T.; Furusawa, K. Tetrahedron 2002, 58, 9257.
(a) Yoshimitsu, Y.; Miyagaki, J.; Oishi, S.; Fujii, N.; Ohno, H. Tetrahedron 2013,
9, 4211; (b) Jung, M. E.; Yi, S. W. Tetrahedron Lett. 2012, 53, 4216; (c) Llaveria,
1
3
(
t, J = 6.4 Hz, 3H). C NMR (100 MHz, CDCl
3
): d 171.0, 170.1,
69.8, 137.5, 124.1, 73.8, 62.6, 50.6, 32.3, 31.9, 29.7, 29.6, 29.5,
9.3, 29.2, 28.9, 23.4, 22.7, 20.9, 20.8, 14.1. HRMS (QTOF): calcd
9.
1
2
6
J.; Díaz, Y.; Matheu, M. I.; Castillón, S. Org. Lett. 2009, 11, 205; (d) Yamamoto, T.;
Hasegawa, H.; Hakogi, T.; Katsumura, S. Org. Lett. 2006, 8, 5569; (e) Chen, G.;
Schmieg, J.; Tsuji, M.; Franck, R. W. Org. Lett. 2004, 6, 4077; (f) Lombardo, M.;
Capdevila, M. G.; Pasi, F.; Trombini, C. Org. Lett. 2006, 8, 3303; (g) Séguin, C.;
Ferreira, F.; Botuha, C.; Chemla, F.; Pérez-Luna, A. J. Org. Chem. 2009, 74, 6986;
(h) Peters, C.; Billich, A.; Ghobrial, M.; Högenauer, K.; Ullrich, T.; Nussbaumer,
P. J. Org. Chem. 1842, 2007, 72; (i) Rai, A. N.; Basu, A. Org. Lett. 2004, 6, 2861; (j)
Chaudhuri, V. D.; Ajish Kumar, K. S.; Dhavale, D. Org. Lett. 2005, 7, 5805; (k)
Torsell, S.; Somfai, P. Org. Biomol. Chem. 2004, 2, 1643; (l) Malik, M.; Ceborska,
M.; Witkowski, G. Tetrahedron Asymmetry 2015, 26, 29; (m) Yamamoto, T.;
Hasegawa, H.; Ishii, S.; Kaji, S.; Masuyama, T.; Harada, S.; Katsumura, S.
Tetrahedron 2008, 64, 11647.
+
for C21
H
37NNaO
5
(M+Na) 406.2569; obs. 406.2578.
4
1
.1.6.4. (2S,3R,E)-2-Acetamidotridec-4-ene-1,3-diyl diacetate
0d.
Colourless solid. Yield: 69%. [
a
]
D
= À21.7 (c 0.35, CHCl
3
).
):
À1
1
IR (KBr): 2923, 2852, 1736, 1656 cm . H NMR (400 MHz, CDCl
3
d 5.75–5.68 (m, 1H), 5.65 (d, J = 9.2 Hz, 1H), 5.32 (dd, J = 14.8,
.2 Hz, 1H), 5.20 (t, J = 6.4 Hz, 1H), 4.38–4.33 (m, 1H), 4.23 (dd,
J = 11.2, 5.6 Hz, 1H), 3.97 (dd, J = 11.2, 3.6 Hz, 1H), 2.01 (s, 3H),
7
1
.99 (s, 3H), 1.92 (s, 3H), 1.18 (br s, 13H), 0.81 (t, J = 7.2 Hz, 3H).
C NMR (100 MHz, CDCl ): d 170.5, 169.5, 169.3, 136.9, 123.6,
3
3.3, 62.1, 50.1, 31.8, 31.3, 29.2, 28.9, 28.8, 28.7, 28.4, 22.9, 22.2,
1
1
0. Geeraert, L.; Mannaerts, G. P.; van Veldhoven, P. P. Biochem. J. 1997, 327, 125.
1. Ageno, G.; Banfi, L.; Cascio, G.; Guanti, G.; Manghisi, E.; Riva, R.; Rocca, V.
Tetrahedron 1995, 29, 8121.
12. For some reviews, see: (a) Prunet, J. Curr. Top. Med. Chem. 2005, 5, 1559; (b)
Brik, A. Adv. Synth. Catal. 2008, 350, 1161; (c) Comprehensive Organic Synthesis;
Zukowska, K.; Grela, K., Eds., 2nd ed., 2014; Vol. 5, p 1257.; (d) O’Leary, D. J.;
O’Neil, G. W. Cross-Metathesis. In Handbook of Metathesis, Set; Grubbs, R. H.,
Wenzel, A. G., O’Leary, D. J., Khosravi, E., Eds.; Wiley-VCH: Weinheim,
Germany, 2015; pp 171–294. http://dx.doi.org/10.1002/9783527674107.ch16.
1
3
7
2
3
+
5
0.7, 20.4, 13.6. HRMS (QTOF): calcd for C19H33NNaO (M+Na)
78.2256; obs. 378.2266.
Acknowledgements
1
3. (a) Ponnapakam, A. P.; Liu, J.; Bhinge, K. N.; Drew, B. A.; Wang, T. L.; Antoon, J.
W.; Nguyen, T. T.; Dupart, P. S.; Wang, Y.; Zhao, M.; Liu, Y.-Y.; Foroozesh, M.;
Beckman, B. S. Bioorg. Med. Chem. 2014, 22, 1412; (b) Chun, J.; Li, G.; Byun, H.-
S.; Bittman, R. J. Org. Chem. 2002, 67, 2600; (c) Chun, J.; He, L.; Byun, H.-S.;
Bittman, R. J. Org. Chem. 2000, 65, 7634; (d) Koskinen, A. M. P.; Koskinen, P. M.
Tetrahedron Lett. 1993, 34, 6765; (e) Lee, J.-M.; Lim, H.-S.; Chung, S.-K.
Tetrahedron Asymmetry 2002, 13, 343; (f) Hoffman, R. V.; Tao, J. J. Org. Chem.
We are thankful to CSIR (Govt. of India) and University of
Kalyani for funds and UGC, New Delhi, for a post-doctoral fellow-
ship to one of us (A.G.).
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Please cite this article in press as: Ghosh, A. ; Chattopadhyay, S. K. Tetrahedron: Asymmetry (2017), http://dx.doi.org/10.1016/j.
tetasy.2017.08.006