Job/Unit: O42603
/KAP1
Date: 21-07-14 16:40:40
Pages: 8
A. Mallick, N. Kumari, R. Roy, A. Palanivel, Y. D. Vankar
FULL PAPER
(87 mg, 87%) as a solid, m.p. 88–90 °C (CHCl3) [ref.[19] m.p. 87–
(+)-epi-Deoxoprosopinine (11): Following a procedure similar to
that described for the synthesis of 10, compound 30 (112 mg) was
transformed into compound 11 (53 mg, 90%) as a white solid, m.p.
88 °C]. Rf (ethyl acetate/methanol, 9:1): 0.5. [α]2D5 = –13.6 (c 0.6,
CHCl3) [ref.[19] [α]2D5 = –14.3 (c 0.54, CHCl )]. IR (neat): ν = 3370,
˜
3
2923, 1021 cm–1. H NMR (400 MHz, CDCl3): δ = 3.84 (dd, J = 56–58 °C (acetone) [ref.[12] m.p. 59 °C (acetone/pentane)]. Rf (ethyl
1
5.7, 13.4 Hz, 1 H), 3.71 (dd, J = 6.4, 13.4 Hz, 1 H), 3.50–3.48 (m,
1 H), 2.58–2.55 (m, 2 H), 2.24 (br. s, 3 H), 2.07–2.03 (m, 2 H),
1.77–1.73 (m, 2 H), 1.42–1.14 (m, 22 H), 0.88 (t, J = 7.0 Hz, 3 H)
ppm. 13C NMR (125 MHz, CDCl3): δ = 67.3, 63.7, 56.9, 52.8, 34.7,
acetate/methanol, 9:1): 0.5. [α]2D5 = +3.9 (c 0.8, CH3OH) [ref.[12]
[α]2D5 = +3.0 (c 0.6, CH OH)]. IR (neat): ν = 3385, 3264, 2952, 2915,
˜
3
2849, 1060 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.97 (br. s, 1
H), 3.92–3.78 (m, 2 H), 2.74 (br. s, 1 H), 2.62–2.61 (m, 1 H), 2.04–
32.9, 32.0, 29.7, 29.6, 29.4, 27.2, 26.1, 22.7, 14.2 ppm. HRMS: 2.00 (m, 1 H), 1.53–1.47 (m, 3 H), 1.29–1.25 (m, 22 H), 0.88 (t, J
calcd. for C18H38NO2 [M + H]+ 300.2903; found 300.2901.
= 7.0 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 66.3, 65.0,
61.1, 56.8, 37.1, 32.0, 31.9, 29.9, 29.7, 29.4, 26.6, 25.9, 22.7,
14.2 ppm. HRMS: calcd. for C18H38NO2 [M + H]+ 300.2903;
found 300.2904.
(2R,3S,6R)-1,3-Bis(benzyloxy)octadecane-2,6-diol (28): Following a
procedure similar to that described for the synthesis of 26, com-
pound 25 (224 mg) was transformed into compound 28 (221 mg,
87%) as an oil. Rf (hexane/ethyl acetate, 7:3): 0.6. [α]2D5 = +10.6 (c
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H and 13C NMR spectra of all new compounds,
2D COSY and NOE spectra for selected compounds.
0.7, CH Cl ). IR (neat): ν = 3316, 2916, 2849, 1465, 1091,
˜
2
2
1
1069 cm–1. H NMR (400 MHz, CDCl3): δ = 7.35–7.27 (m, 10 H),
4.55 (s, 2 H), 4.54 (s, 2 H), 3.93–3.89 (m, 1 H), 3.64 (dd, J = 3.4,
9.5 Hz, 1 H), 3.59–3.51 (m, 3 H), 1.80–1.72 (m, 2 H), 1.58–1.49 (m,
2 H), 1.46–1.40 (m, 3 H), 1.25 (s, 19 H), 0.87 (t, J = 7.0 Hz, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 138.2, 137.9, 128.4, 127.9,
127.8, 79.5, 73.4, 72.2, 71.9, 71.5, 71.1, 38.7, 37.5, 32.7, 31.9, 29.6,
29.3, 27.8, 26.0, 25.6, 22.6, 14.0 ppm. HRMS: calcd. for C32H51O4
[M + H]+ 499.3787; found 499.3782; calcd. for C32H50NaO4 [M +
Na]+ 521.3607; found 521.3602.
Acknowledgments
The authors thank the Department of Science and Technology
(DST), New Delhi, for the J. C. Bose National Fellowship (grant
to Y. D. V., grant number JCB/SR/S2/JCB-26/2010), and the Coun-
cil of Scientific and Industrial Research (CSIR), New Delhi (grant
number 02(0124)/13/EMR-II), for financial support through. A. M.
also thanks CSIR for a Senior Research Fellowship.
(2R,3S,6R)-1,3-Bis(benzyloxy)octadecane-2,6-diyl Dimethanesulfon-
ate (29): Diol 12 (471 mg, 0.945 mmol) was dissolved in dry CH2Cl2
(5 mL), and then triethylamine (0.33 mL, 2.362 mmol), meth-
anesulfonyl chloride (0.18 mL, 2.362 mmol), and a catalytic
amount of DMAP (23 mg, 0.189 mmol) were added at 0 °C. The
mixture was stirred at room temperature for 30 min, then it was
quenched with ice-cold water (5 mL). The organic layer was washed
with water (3ϫ 10 mL), followed by brine. The organic layer was
dried with Na2SO4, and concentrated in vacuo. The residue was
purified by column chromatography to give 29 (411 mg, 66%) as
an oil. Rf (hexane/ethyl acetate, 4:1): 0.5. [α]2D5 = –8.5 (c 0.7,
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1818.
CH Cl ). IR (neat): ν = 2925, 2853, 1455, 1353, 1174, 1027,
˜
2
2
1
909 cm–1. H NMR (500 MHz, CDCl3): δ = 7.36–7.29 (m, 10 H),
4.90–4.87 (m, 1 H), 4.69–4.66 (m, 2 H), 4.54–4.49 (m, 3 H), 3.74–
3.66 (m, 3 H), 3.10 (s, 3 H), 2.94 (s, 3 H), 1.90–1.84 (m, 1 H), 1.69–
1.57 (m, 6 H), 1.25 (s, 19 H), 0.87 (t, J = 7.0 Hz, 3 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 137.4, 137.2, 128.5, 128.4, 128.2,
127.9, 127.8, 83.8, 82.4, 77.9, 73.5, 72.8, 68.6, 38.6, 34.6, 31.8, 30.1,
29.6, 29.5, 29.4, 29.3, 26.1, 24.9, 22.6, 14.1 ppm. HRMS: calcd. for
C34H54NaO8S2 [M + Na]+ 677.3158; found 677.3156.
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(2S,3S,6R)-1-Benzyl-3-(benzyloxy)-2-(benzyloxymethyl)-6-dodecyl-
piperidine (30): Dimesylate 29 (170 mg, 0.299 mmol) was dissolved
in benzylamine (5 mL), and the mixture was heated at 80 °C for
5 h. The solution was diluted with Et2O (10 mL), and washed with
HCl (1 n), water, and brine. The organic layer was dried with
Na2SO4. The crude product was purified by column chromatog-
raphy to give 30 (122 mg, 82%) as an oil. Rf (hexane/ethyl acetate,
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19:1): 0.5. [α]2D5 = +10.9 (c 1.1, CH Cl ). IR (neat): ν = 2924, 2852,
˜
2
2
1453, 1092, 1027 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.34–7.17
(m, 15 H), 4.55 (d, J = 11.9 Hz, 1 H), 4.45 (d, J = 11.9 Hz, 1 H),
4.37 (dd, J = 11.9, 15.2 Hz, 2 H), 4.04 (d, J = 15.9 Hz, 1 H), 3.81
(d, J = 15.9 Hz, 1 H), 3.70–3.67 (m, 2 H), 3.63–3.60 (m, 1 H), 3.20–
3.18 (m, 1 H), 2.59–2.57 (m, 1 H), 1.92–1.88 (m, 1 H), 1.71–1.69
(m, 1 H), 1.54–1.45 (m, 2 H), 1.28–1.10 (m, 22 H), 0.87 (t, J =
7.0 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 142.7, 139.2,
138.6, 128.3, 128.0, 127.9, 127.8, 127.5, 127.3, 126.2, 75.0, 73.2,
70.8, 70.4, 62.8, 60.2, 53.6, 32.7, 32.0, 29.9, 29.7, 29.4, 27.5, 25.8,
24.1, 22.5, 14.2 ppm. HRMS: calcd. for C39H56NO2 [M + H]+
570.4311; found 570.4316.
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