NЈ-Substituted 2-Imino-1,3-oxazolidines
41.4 (C-4), 40.3 (C-7), 36.5 (C-4Ј), 35.8 (C-8), 35.0 (C-2ЈЈ), 29.9 (3Ј- 3.73 (5-H), 3.68 (5Ј-H), 3.59 (2Ј-H), 3.31 (6-OCH3), 3.20 (11-H),
NCH3), 21.8 (3ЈЈ-CH3), 21.8 (6-CH3), 21.3 (5Ј-CH3), 20.9 (C-14),
3.12 (3ЈЈ-OCH3), 3.05 (4ЈЈ-H), 2.89 (3Ј-H), 2.85 (3Ј-NCH3), 2.83 (2-
19.7 (8-CH3), 18.7 (5ЈЈ-CH3), 16.3 (12-CH3), 15.4 (2-CH3), 14.1 H), 2.29 (2ЈЈ-Ha), 2.22 (8-H), 2.01 (4Ј-Ha), 1.88 (4-H), 1.88 (7-Ha),
(10-CH3), 11.4 (15-CH3), 9.9 (4-CH3) ppm. HRMS (ES): calcd. for 1.87 (14-Ha), 1.58 (2ЈЈ-Hb), 1.58 (14-Hb), 1.43 (7-Hb), 1.42 (4Ј-Hb),
C45H76N3O13S [M + H]+ 898.5099; found 898.5113.
1.35 (6-CH3), 1.29 (5ЈЈ-CH3), 1.28 (5Ј-CH3), 1.23 (2-CH3), 1.20
(3ЈЈ-CH3), 1.18 (12-CH3), 1.16 (10-CH3), 1.10 (8-CH3), 0.92 (4-
CH3), 0.89 (15-CH3) ppm. 13C NMR (125 MHz, CDCl3): benzyl:
δ = 138.1 (C), 128.2 (2 CH), 127.7 (2 CH), 126.4 (CH), 49.5
(CH2) ppm; macrolide: δ = 179.6 (C-1), 177.4 (C-9), 157.4 (C=N),
99.5 (C-1Ј), 95.8 (C-1ЈЈ), 81.0 (C-2Ј), 80.2 (C-5), 79.1 (C-6), 78.6
(C-13), 77.8 (C-4ЈЈ), 77.0 (C-3), 74.3 (C-12), 73.1 (C-3ЈЈ), 73.0 (C-
11), 70.2 (C-5Ј), 66.0 (C-5ЈЈ), 62.8 (C-3Ј), 51.6 (6-OCH3), 49.5 (3ЈЈ-
OCH3), 45.5 (C-10), 44.6 (C-2), 40.8 (C-4), 40.0 (C-4Ј), 36.4 (C-7),
35.6 (C-8), 34.8 (C-2ЈЈ), 32.1 (3Ј-NCH3), 21.5 (3ЈЈ-CH3), 21.0 (6-
CH3), 20.8 (C-14), 20.6 (5Ј-CH3), 19.5 (8-CH3), 18.3 (5ЈЈ-CH3),
16.2 (12-CH3), 15.4 (2-CH3), 14.0 (10-CH3), 11.2 (15-CH3), 8.9 (4-
CH3) ppm. HRMS (ES): calcd. for C45H73N3O13 [M + H]+
864.5184; found 864.5184.
3Ј-N-(Benzylthiocarbamoyl)-3Ј-N-demethyl-6-O-methylhomoeryth-
romycin A (8): According to step 1 of the stepwise general pro-
cedure, the reaction of 5 (0.36 g, 0.48 mmol) afforded 8 (0.42 g,
1
65%) as a white foam. H NMR (500 MHz, DMSO): benzyl: δ =
7.41 (2 CH), 7.35 (2 CH), 7.19 (CH), 4.83 (CH2) ppm; macrolide:
δ = 8.30 (9a-NH), 4.77 (1ЈЈ-H), 5.04 (13-H), 4.42 (1Ј-H), 2.95 (10-
H), 3.61 (3-H), 4.06 (5ЈЈ-H), 3.64 (5-H), 3.79 (5Ј-H), 3.20 (2Ј-H),
2.96 (6-OCH3), 3.23 (3ЈЈ-OCH3), 3.64 (11-H), 2.90 (4ЈЈ-H), 2.79 (2-
H), 2.89 (3Ј-H), 2.26 (2ЈЈ-Ha), 2.54 (8-H), 1.76 (7-Ha), 1.85 (4-H),
1.63 (4Ј-Ha), 1.81 (14-Ha), 1.53 (2ЈЈ-Hb), 1.39 (14-Hb), 1.47 (7-Hb),
1.33 (4Ј-Hb), 1.30 (6-CH3), 2.91 (3Ј-NCH3), 1.01 (2-CH3), 1.17 (5ЈЈ-
CH3), 1.12 (3ЈЈ-CH3), 1.08 (5Ј-CH3), 1.02 (10-CH3), 1.01 (12-CH3),
1.04 (8-CH3), 1.03 (4-CH3), 0.74 (15-CH3) ppm. 13C NMR
(125 MHz, DMSO): benzyl: δ = 139.9 (C), 128.8 (2 CH), 128.0 (2
CH), 127.1 (CH), 48.3 (CH2) ppm; macrolide: δ = 184 (C=S), 175
(C-1), 218.5 (C-9), 102.0 (C-1Ј), 95.7 (C-1ЈЈ), 79.1 (C-5), 77.9 (C-
6), 75.9 (C-13), 77.2 (C-4ЈЈ), 76.9 (C-3), 74.2 (C-12), 72.4 (C-3ЈЈ),
71.0 (C-2Ј), 68.9 (C-11), 66.5 (C-5Ј), 65.0 (C-5ЈЈ), 60 (C-3Ј), 50.2
(6-OCH3), 49.0 (3ЈЈ-OCH3), 39.2 (C-10), 44.3 (C-2), 38.5 (C-4),
39.0 (C-7), 35.6 (C-4Ј), 43.4 (C-8), 34.8 (C-2ЈЈ), 30 (3Ј-NCH3), 20.8
(3ЈЈ-CH3), 19.9 (6-CH3), 21.2 (5Ј-CH3), 20.9 (C-14), 17.7 (8-CH3),
18.9 (5ЈЈ-CH3), 17.0 (12-CH3), 15.7 (2-CH3), 11.8 (10-CH3), 10.5
(15-CH3), 9.0 (4-CH3) ppm. HRMS (ES): calcd. for C45H75N2O13S
[M + H]+ 883.4990; found 883.4987.
2Ј-O,3Ј-N-(Benzylcarbonimidoyl)-3Ј-N-demethyl-6-O-methyleryth-
romycin A (11): According to step 2 of the stepwise general pro-
cedure, the reaction of 8 (0.35 g, 0.40 mmol) afforded 11 (0.20 g,
59%) as a white foam. IR (KBr): ν = 3452, 2972, 2941, 2884, 2826,
˜
2088, 1734, 1704, 1456, 1423, 1377, 1352, 1325, 1287, 1242, 1172,
1127, 1081, 1055, 1000, 903, 854, 751, 700, 628 cm–1. 1H NMR
(500 MHz, CDCl3): benzyl: δ = 7.33 (2 CH), 7.26 (2 CH), 7.18
(CH), 4.46 (CH2) ppm; macrolide: δ = 5.07 (13-H), 4.92 (1ЈЈ-H),
4.89 (1Ј-H), 3.97 (5ЈЈ-H), 3.74 (11-H), 3.72 (3-H), 3.70 (5Ј-H), 3.66
(5-H), 3.56 (2Ј-H), 3.18 (3ЈЈ-OCH3), 3.06 (4ЈЈ-H), 3.04 (6-OCH3),
3.02 (10-H), 2.82 (3Ј-H), 2.77 (3Ј-NCH3), 2.89 (2-H), 2.59 (8-H),
2.35 (2ЈЈ-Ha), 1.98 (4Ј-Ha), 1.93 (14-Ha), 1.91 (4-H), 1.81 (7-Ha),
1.58 (2ЈЈ-Hb), 1.77 (14-Hb), 1.61 (7-Hb), 1.43 (4Ј-Hb), 1.40 (6-CH3),
1.29 (5ЈЈ-CH3), 1.29 (5Ј-CH3), 1.20 (2-CH3), 1.24 (3ЈЈ-CH3), 1.14
(12-CH3), 1.12 (10-CH3), 1.14 (8-CH3), 1.02 (4-CH3), 0.85 (15-
CH3) ppm. 13C NMR (125 MHz, CDCl3): benzyl: δ = 142.2 (C),
128.5 (2 CH), 127.8 (2 CH), 126.6 (CH), 50.4 (CH2) ppm; macro-
lide: δ = 221.2 (C-9), 176.0 (C-1), 156.9 (C=N), 100.0 (C-1Ј), 96.7
(C-1ЈЈ), 82.1 (C-5), 80.9 (C-2Ј), 79.2 (C-3), 78.4 (C-6), 78.2 (C-4ЈЈ),
77.1 (C-13), 74.6 (C-12), 73.2 (C-3ЈЈ), 70.6 (C-5Ј), 69.5 (C-11), 66.3
(C-5ЈЈ), 63.0 (C-3Ј), 51.1 (6-OCH3), 49.8 (3ЈЈ-OCH3), 45.7 (C-8),
45.3 (C-2), 39.4 (C-7), 38.8 (C-4), 37.7 (C-10), 36.8 (C-4Ј), 35.3 (C-
2ЈЈ), 32.5 (3Ј-NCH3), 21.8 (3ЈЈ-CH3), 21.4 (C-14), 20.0 (6-CH3),
21.3 (5Ј-CH3), 18.7 (5ЈЈ-CH3), 18.4 (8-CH3), 16.5 (12-CH3), 16.3
(2-CH3), 12.7 (10-CH3), 10.9 (15-CH3), 9.1 (4-CH3) ppm. HRMS
(ES): calcd. for C45H72N2O13 [M + H]+ 849.5113; found 849.5133.
3Ј-N-(Benzylthiocarbamoyl)-3Ј-N-demethyl-6-O-methyl-9-deoxo-9a-
aza-9a-homoerythromycin A (9): According to step 1 of the stepwise
general procedure, the reaction of 6 (0.1 g, 0.14 mmol) afforded 9
(0.11 g, 85 %) as a white foam. 1H NMR (500 MHz, DMSO):
benzyl: δ = 7.41 (2 CH), 7.36 (2 CH), 7.20 (CH), 4.79 (CH2) ppm;
macrolide: δ = 8.30 (9a-NH), 4.84 (1ЈЈ-H), 4.73 (13-H), 4.43 (1Ј-
H), 2.65 (10-H), 4.18 (3-H), 4.11 (5ЈЈ-H), 3.54 (5-H), 3.79 (5Ј-H),
3.22 (2Ј-H), 3.31 (6-OCH3), 3.26 (3ЈЈ-OCH3), 3.43 (11-H), 2.91 (4ЈЈ-
H), 2.65 (2-H), 2.62 (3Ј-H), 2.24 (2ЈЈ-Ha), 1.88 (8-H), 1.54 (7-Ha),
1.88 (4-H), 1.36 (4Ј-Ha), 1.76 (14-Ha), 1.50 (2ЈЈ-Hb), 1.28 (14-Hb),
1.33 (7-Hb), 1.36 (4Ј-Hb), 1.18 (6-CH3), 2.20 (3Ј-NCH3), 1.07 (2-
CH3), 1.15 (5ЈЈ-CH3), 1.12 (3ЈЈ-CH3), 1.06 (5Ј-CH3), 0.94 (10-CH3),
1.01 (12-CH3), 0.85 (8-CH3), 0.94 (4-CH3), 0.78 (15-CH3) ppm. 13
C
NMR (125 MHz, DMSO): benzyl: δ = 139.9 (C), 128.2 (2 CH),
128.0 (2 CH), 127.9 (CH), 48.3 (CH2) ppm; macrolide: δ = 182
(C=S), 177.1 (C-1), 68.7 (C-9), 102.2 (C-1Ј), 94.4 (C-1ЈЈ), 82.5 (C-
5), 73.6 (C-6), 76.3 (C-13), 77.4 (C-4ЈЈ), 77.1 (C-3), 72.7 (C-12),
72.5 (C-3ЈЈ), 70.9 (C-2Ј), 74.9 (C-11), 66.5 (C-5Ј), 64.7 (C-5ЈЈ), 60
(C-3Ј), 48.3 (6-OCH3), 48.8 (3ЈЈ-OCH3), 61.4 (C-10), 44.6 (C-2),
41.6 (C-4), 41.8 (C-7), 35.7 (C-4Ј), 26.1 (C-8), 34.7 (C-2ЈЈ), 29.9 (3Ј-
NCH3), 21.0 (3ЈЈ-CH3), 27.4 (6-CH3), 21.2 (5Ј-CH3), 20.9 (C-14),
22.1 (8-CH3), 18.5 (5ЈЈ-CH3), 17.7 (12-CH3), 14.7 (2-CH3), 6.7 (10-
CH3), 11.0 (15-CH3), 9.1 (4-CH3) ppm. HRMS (ES): calcd. for
C45H78N3O12S [M + H]+ 884.5306; found 884.5295.
2Ј-O,3Ј-N-(Benzylcarbonimidoyl)-3Ј-N-demethyl-9-deoxo-9a-
methyl-9a-aza-9a-homoerythromycin A (12): According to step 2 of
the stepwise general procedure, the reaction of 9 (0.10 g,
0.11 mmol) afforded 12 (0.061 g, 66%) as a white foam. IR (KBr):
ν = 3508, 2971, 2935, 2875, 2828, 2645, 2113, 1705, 1462, 1423,
˜
1379, 1345, 1322, 1282, 1255, 1181, 1127, 1080, 1055, 1004, 957,
902, 857, 799, 731, 698 cm–1. 1H NMR (500 MHz, CDCl3): benzyl:
δ = 7.32 (2 CH), 7.26 (2 CH), 7.18 (CH), 4.45 (CH2) ppm; macro-
lide: δ = 5.09 (1ЈЈ-H), 4.89 (1Ј-H), 4.68 (13-H), 4.19 (3-H), 4.02
(5ЈЈ-H), 3.68 (5Ј-H), 3.65 (11-H), 3.61 (5-H), 3.61 (2Ј-H), 3.17 (3ЈЈ-
OCH3), 3.05 (4ЈЈ-H), 2.79 (3Ј-NCH3), 2.77 (2-H), 2.71 (10-H), 2.54
(9-Ha), 2.42 (3Ј-H), 2.33 (9a-NCH3), 2.32 (2ЈЈ-Ha), 2.07 (9-Hb),
1.97 (4Ј-Ha), 1.96 (8-H), 1.95 (4-H), 1.87 (14-Ha), 1.72 (7-Ha), 1.58
2Ј-O,3Ј-N-(Benzylcarbonimidoyl)-3Ј-N-demethyl-6-O-methyl-9a-
aza-9a-homoerythromycin A (10): According to step 2 of the step-
wise general procedure, the reaction of 7 (0.2 g, 0.22 mmol) af-
forded 10 (0.14 g, 74%) as a white foam. IR (KBr): ν = 3448, 2973, (2ЈЈ-Hb), 1.48 (14-Hb), 1.42 (4Ј-Hb), 1.32 (6-CH3), 1.30 (5ЈЈ-CH3),
˜
2935, 2879, 1705, 1658, 1526, 1456, 1424, 1379, 1325, 1281, 1237,
1181, 1125, 1079, 1054, 1004, 956, 903, 803, 732, 698, 630 cm–1. 1H
NMR (500 MHz, CDCl3): benzyl: δ = 7.34 (2 CH), 7.25 (2 CH),
7.18 (CH), 4.44 (CH2) ppm; macrolide: δ = 6.16 (9a-NH), 4.89 (1Ј-
1.23 (7-Hb), 1.23 (5Ј-CH3), 1.20 (3ЈЈ-CH3), 1.18 (2-CH3), 1.11 (10-
CH3), 1.08 (12-CH3), 0.94 (4-CH3), 0.93 (8-CH3), 0.89 (15-
CH3) ppm. 13C NMR (125 MHz, CDCl3): benzyl: δ = 141.6 (C),
128.1 (2 CH), 127.5 (2 CH),126.4 (CH), 49.8 (CH2) ppm; macro-
H), 4.84 (1ЈЈ-H), 4.67 (13-H), 4.16 (10-H), 4.12 (3-H), 4.02 (5ЈЈ-H), lide: δ = 178.7 (C-1), 157.0 (C=N), 99.8 (C-1Ј), 95.2 (C-1ЈЈ), 84.8
Eur. J. Org. Chem. 2011, 2507–2518
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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