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oil, eluent for column chromatography: EtOAc/hexane (1/9, v/v);
[a]2D8 ¼ +23.33 (c 1.48, CHCl3); Rf 0.63 (2/3 EtOAc/hexane); 1H
NMR (400 MHz, CDCl3): d 2.99–3.00 (m, 2H), 3.39 (dd, J ¼ 5.5, 10
Hz, 1H), 3.67–3.71 (m, 2H), 3.85–3.88 (m, 1H), 3.92 (dd, J ¼ 3.5, 5.5
Hz, 1H), 4.21–4.23 (m, 1H), 4.27 (d, J ¼ 11.7, 1H), 4.34–4.46 (m,
6H), 4.52–4.74 (m, 6H), 5.16–5.20 (m, 1H), 5.66 (d, J ¼ 4 Hz, 2H),
7.18–7.26 (m, 25H). 13C NMR (100 MHz, CDCl3): d 22.1 (CH2), 54.4
(CH2), 69.1 (CH2), 69.1 (CH), 70.7 (CH2), 71.0 (CH2), 73.2 (CH), 73.6
(CH2), 73.6 (CH2), 74.5 (CH2), 78.2 (Cq), 80.0 (CH), 81.0 (CH), 84.5
(CH), 85.5 (Cq), 127.8–128.7, (ArC), 129.1 (CH), 129.6 (CH), 137.3
(ArCq), 137.5 (ArCq), 137.6 (ArCq), 138.3 (ArCq), 138.4 (ArCq). IR
(neat, cmꢃ1) 3410, 3019, 1216, 1180, 699, 669; ESI-HRMS m/z [M +
Na]+: calcd for C48H51ClO9S 861.2835, measured 861.2820.
triazole (29d). Colorless oil, eluent for column chromatography:
EtOAc/hexane (3/7, v/v); [a]2D8 ¼ ꢃ10.48 (c 1.4, CH3OH); Rf 0.60
(1/9 EtOAc/hexane); 1H NMR (400 MHz, CDCl3): d 1.50–1.65 (m,
9H), 1.91–2.02 (m, 4H), 3.37–3.48 (m, 2H), 3.82 (dd, J ¼ 8.1, 10.5
Hz, 1H), 4.01–4.05 (m, 1H), 4.39–4.53 (m, 5H), 4.57–4.64 (m,
2H), 4.71 (d, J ¼ 5 Hz, 1H), 4.82–4.87 (m, 1H), 4.95–5.03 (m, 1H),
5.26–5.30 (dd, J ¼ 6.4, 12.7 Hz, 1H), 7.15–7.28 (m, 15H). 13C
NMR (100 MHz, CDCl3): d 16.5 (CH3), 17.8 (CH3), 25.2 (CH2),
25.8 (CH3), 26.7 (CH2), 39.8 (CH2), 60.4 (CH), 69.4 (CH2), 70.0
(CH), 71.8 (CH2), 72.7 (CH2), 73.5 (CH2), 81.7 (CH), 120.5 (CH),
124.2 (CH), 127.7–128.7 (ArC), 131.7 (Cq), 134.7 (Cq), 137.0
(ArCq), 137.5 (ArCq), 137.6 (ArCq), 138.0 (Cq), 142.6 (Cq). IR (neat,
cmꢃ1) 3399, 3019, 1180, 699, 669; ESI-HRMS m/z [M + H]+: calcd
for C37H43N3O3 578.3377, measured 578.3376.
(4S,5R,6S)-4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-(cyclohex-
2-enyl)-5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]triazole (29e). Color-
less oil, eluent for column chromatography: EtOAc/hexane (1/4,
v/v); [a]2D8 ¼ ꢃ35.85 (c 5.55, CHCl3); Rf 0.45 (2/3 EtOAc/hexane);
1H NMR (400 MHz, CDCl3): d 1.49–1.80 (m, 4H), 1.92–2.00 (m,
3H), 3.56–3.62 (m, 1H), 3.80–3.85 (m, 1H), 4.01–4.05 (m, 1H),
4.40–4.69 (m, 7H), 4.76–4.86 (m, 2H), 5.68–5.85 (m, 2H), 7.15–
7.28 (m, 15H). 13C NMR (100 MHz, CDCl3): d 21.0, 21.2 (CH2),
25.0, 25.1 (CH2), 30.4 (CH2), 33.6, 33.7 (CH), 60.0, 60.0 (CH), 69.4,
69.5 (CH2), 70.6, 70.7 (CH), 72.6 (CH2), 72.8, 72.9 (CH2), 73.4, 73.5
(CH2), 82.1, 82.2 (CH), 127.7–128.7 (ArC), 129.5 (CH), 134.5, 134.6
(ArCq), 137.1 (ArCq), 137.7, 137.8 (ArCq), 138.0 (Cq), 146.5, 146.6
(Cq). IR (neat, cmꢃ1) 3407, 3019, 1216, 699, 669; ESI-HRMS m/z [M
+ H]+: calcd for C33H35N3O3 522.2751, measured 522.2767.
(4S,5R,6S)-4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-cinnamyl-
5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]triazole (29f). Brown oil,
(4S,5R,6S)-3-Allyl-4,5-bis(Benzyloxy)-6-(benzyloxymethyl)-5,6-
dihydro-4H-pyrrolo[1,2-c][1,2,3]triazole (29a). Colorless oil,
eluent for column chromatography: EtOAc/hexane (1/4, v/v);
1
[a]2D8 ¼ ꢃ11.85 (c 0.33, CH3OH); Rf 0.71 (1/1 EtOAc/hexane); H
NMR (400 MHz, CDCl3): d 3.46–3.59 (m, 2H), 3.88–3.92 (m, 1H),
4.11 (dd, J ¼ 4.4 Hz, 1H), 4.48–4.81 (m, 8H), 4.90–4.95 (m, 1H),
5.09–5.13 (m, 2H), 5.92–6.02 (m, 1H), 7.25– 7.33 (m, 15H). 13C
NMR (100 MHz, CDCl3): d 30.6 (CH2), 60.5 (CH), 69.4 (CH), 69.7
(CH), 72.0 (CH2), 72.7 (CH2), 73.5 (CH2), 81.6 (CH), 117.0 (CH2),
127.8–128.8 (ArC), 134.9 (CH), 135.3 (Cq), 137.0 (ArCq), 137.5
(ArCq), 138.0 (ArCq), 141.0 (Cq). IR (neat, cmꢃ1) 3388, 3018, 1216,
771, 669; ESI-HRMS m/z [M + H]+: calcd for C30H31N3O3
482.2438, measured 482.2437.
(4S,5R,6S)-4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-((E)-but-
2-enyl)-5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]triazole (29b). Color-
less oil, eluent for column chromatography: EtOAc/hexane (1/4,
v/v); [a]2D8 ¼ +50.5050 (c 0.02, CH3OH); Rf 0.52 (2/3 EtOAc/
hexane); 1H NMR (400 MHz, CDCl3): d 1.57–1.59 (m, 3H),
3.33–3.45 (m, 2H), 3.82 (dd, J ¼ 8.1, 10.5 Hz, 1H), 4.03 (dd, J ¼
4.5, 10.5 Hz, 1H), 4.40–4.71 (m, 8H), 4.82–4.87 (m, 1H), 5.46–
5.52 (m, 2H), 7.17–7.27 (m, 15H). 13C NMR (100 MHz, CDCl3):
d 60.5 (CH2), 69.4 (CH), 69.8 (CH), 72.0 (CH2), 72.7 (CH2), 73.5
(CH2), 81.6 (CH), 127.5 (CH), 128.5 (CH), 127.7–128.78 (ArC),
127.5 (CH), 128.4 (CH), 135.0 (Cq), 137.0 (ArCq), 137.6 (ArCq),
138.0 (ArCq), 141.9 (Cq). IR (neat, cmꢃ1) 3378, 3014, 1199, 776,
660; ESI-HRMS m/z [M + H]+: calcd for C31H33N3O3 496.2595,
measured 496.2595.
eluent for column chromatography: EtOAc/hexane (1/4, v/v); [a]D28
¼
+275.27 (c 7.44, CH3OH); Rf 0.9 (1/5 EtOAc/hexane); 1H NMR (400
MHz, CDCl3): d 3.48–3.68 (m, 1H), 3.94 (dd, J ¼ 9.1, 10.6 Hz), 4.10
(dd, J ¼ 3.8, 10.7 Hz), 4.34–4.72 (m, 9H), 4.80–4.94 (m, 2H), 5.28 (d,
J ¼ 5.0 Hz), 7.12–7.27 (m, 20H). 13C NMR (100 MHz, CDCl3): d 29.9
(CH2), 61.0 (CH), 69.5 (CH2), 69.6 (CH), 72.1 (CH2), 72.1 (CH2), 73.5
(CH2), 80.9 (CH), 126.4 (Cq), 127.8–128.8 (ArC + 2 ꢂ CH), 135.3
(ArCq), 135.9 (ArCq), 136.9 (ArCq), 138.0 (ArCq + Cq), 138.1 (ArCq). IR
(neat, cmꢃ1) 3417, 3010, 1215, 771, 669; ESI-HRMS m/z [M + H]+:
calcd for C36H35N3O3 558.2751, measured 558.2750.
(4S,5R,6S)-4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-(3-meth-
ylbut-2-enyl)-5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]triazole (29c).
Colorless oil, eluent for column chromatography: EtOAc/hexane
(11/39, v/v); [a]2D8 ¼ ꢃ8.29 (c 0.80, CHCl3); Rf 0.36 (2/3 EtOAc/
hexane); 1H NMR (400 MHz, CDCl3): d 1.71–1.75 (m, 6H),
3.50–3.53 (m, 2H), 3.92 (dd, J ¼ 4.5, 10.5 Hz, 1H), 4.52 (dd, J ¼ 5,
7.0 Hz, 1H), 4.56–4.64 (m, 4H), 4.71 (dd, J ¼ 11.8, 14.4 HZ, 2H),
4.80 (d, J ¼ 5 Hz, 1H), 4.92–4.97 (m, 1H), 5.34–5.38 (m, 1H),
7.26–7.37 (m, 15H). 13C NMR (100 MHz, CDCl3): d 18.2 (CH3),
25.2 (CH2), 25.8 (CH3), 60.4 (CH), 69.4 (CH2), 70.0 (CH), 71.9
(CH2), 72.8 (CH2), 73.5 (CH2), 81.7 (CH), 120.7 (CH), 127.7–128.8
(ArC), 133.8 (Cq), 134.8 (Cq), 137.1 (ArCq), 137.6 (ArCq), 138.1
(ArCq), 142.6 (Cq). IR (neat, cmꢃ1) 3410, 3016, 1201, 1212, 771,
659; ESI-HRMS m/z [M + H]+: calcd for C32H35N3O3 510.2751,
measured 510.2727.
(2R,3S,E)-1,3-Bis(benzyloxy)-6-((4S,5R,6S)-4,5-bis(benzyloxy)-
6-(benzyloxymethyl)-5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]triazol-
3-yl)hex-4-en-2-ol (29g). Colorless oil, eluent for column chro-
matography: EtOAc/hexane (3/7, v/v); [a]2D8 ¼ +3.29 (c 0.304,
CH3OH); Rf 0.41 (3/2 EtOAc/hexane); 1H NMR (400 MHz,
CDCl3): d 3.54–3.78 (m, 4H), 3.87–3.97 (m, 3H), 4.04–4.16 (m,
3H), 4.23–4.26 (m, 1H), 4.33 (t, J ¼ 6.6 Hz, 1H), 4.50–4.55 (m,
4H), 4.63–4.73 (m, 6H), 5.87–5.98 (m, 1H), 6.17–6.29 (m, 1H),
7.28–7.38 (m, 25H). 13C NMR (100 MHz, CDCl3): d 29.9 (CH2),
60.0 (CH), 66.6 (CH2), 68.4 (CH2), 70.9 (CH2), 71.4 (CH2), 72.2
(CH), 72.8 (CH2), 73.7 (CH2), 74.1 (CH2), 75.2 (CH2), 75.9 (CH),
80.9 (CH), 117.8 (CH), 123.4 (CH), 127.7–129.0 (ArC), 131.1
(CH), 136.0 (Cq), 136.9 (ArCq), 137.2 (ArCq), 137.7 (ArCq), 138.2
(2 ꢂ ArCq), 140.4 (Cq). IR (neat, cmꢃ1) 3410, 3015, 1198, 1156,
780, 669; ESI-HRMS m/z [M + H]+: calcd for C47H49N3O6
752.3694, measured 752.3698.
(4S,5R,6S)-4,5-Bis(benzyloxy)-6-(benzyloxymethyl)-3-((2E,6E)-
3-methylocta-2,6-dienyl)-5,6-dihydro-4H-pyrrolo[1,2-c][1,2,3]
This journal is © The Royal Society of Chemistry 2016
RSC Adv., 2016, 6, 13014–13026 | 13023