基于点击化学反应的半乳糖糖基化马蹄金素衍生物的合成及抗HBV活性

doi:10.7503/cjcu20160098

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (7): 1307.doi: 10.7503/cjcu20160098

基于点击化学反应的半乳糖糖基化马蹄金素衍生物的合成及抗HBV活性

袁洁^1,⁴, 刘青川², 徐广灿^1,³, 梁光义^1,³(), 徐必学¹

1. 贵州省中国科学院天然产物化学重点实验室, 贵阳 550002
2. 中国人民解放军第三○二医院, 北京 100039
3. 贵阳中医学院, 贵阳 550002
4. 新疆医科大学厚博学院, 克拉玛依 834000

收稿日期:2016-02-17 接受日期:2016-06-15 出版日期:2016-07-10 发布日期:2016-06-15
基金资助:
国家自然科学基金(批准号: 81360472)和“西部之光”人才项目(2014年)资助

Synthesis and Anti-HBV Activity Evaluation of the Galactopyranosyl Derivatives of MTS Based on Click Reaction^†

YUAN Jie^1,⁴, LIU Qingchuan², XU Guangcan^1,³, LIANG Guangyi^1,^3,^*, XU Bixue^1,^*()

1. The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guiyang 550002, China
2. 302 Hospital of PLA, Beijing 100039, China
3. Guiyang College of Traditional Chinese Medicine, Guiyang 550002, China
4. College of Houbo, Xinjiang Medical University, Klamayi 834000, China

Received:2016-02-17 Accepted:2016-06-15 Online:2016-07-10 Published:2016-06-15
Contact: LIANG Guangyi,XU Bixue E-mail:guangyi_liang@126.com;bixue_xu@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.81360472) and the Western Light Talent Culture Project, China(2014)

摘要/Abstract

摘要：

以D-半乳糖和二缩三乙二醇为原料, 经乙酰化、糖基化和叠氮化钠取代等反应合成了带叠氮连接臂的半乳糖配基, 通过点击化学反应将其与炔丙基修饰的马蹄金素(MTS)衍生物进行连接, 设计合成了6个具有潜在肝靶向性的半乳糖糖基化MTS衍生物. 通过¹H NMR, ¹³C NMR, ¹H-¹H COSY, HMQC, DEPT和ESI-MS对其结构进行了表征; 采用HepG2 2.2.15细胞模型初步评价了目标化合物的抗乙型肝炎病毒(HBV)活性. 结果表明, 所有目标化合物对HBV DNA的复制均有抑制作用, 且具有一定的量效关系; 化合物15f在50 μg/mL浓度下对HepG2 2.2.15细胞株的抑制率为83%, 具有进一步研究的价值.

关键词: 肝靶向, 半乳糖, 马蹄金素衍生物, 点击化学, 抗HBV活性

Abstract:

Matijin-Su [N-(N-benzoyl-L-phenylalanyl)-O-acetyl-L-phenylalanol, MTS], a dipeptide derivative, was isolated from a Chinese ethnic drug Matijin(Dichondra repens Forst.) which has been widely used in the treatment of chronic liver disease as folk medicine in China. A series of MTS derivatives with anti-hepatitis B virus(HBV) activitiy was synthesized by structural modification of MTS. One of MTS derivatives named “Tyrophentide” had been finished pre-clinical research and has been approved to do clinical study of phase Ⅰ by China Food and Drug Administration(CFDA). The preliminary pharmacokinetic experiments showed that it was widely distributed in many organs, and the concentration in liver was low. To improve the concentration in liver lesion tissue and increase the anti-HBV activity of MTS derivatives, a series of hepatic targeting galactopyranosyl derivatives of MTS 15a—15f was designed according to asialoglycoprotein receptor(ASGP-R) mediation and synthesized. Starting from unexpensive and commercially available galactose and triethylene glycol, the glycosyl donor with azide linker was achieved via acetylation, glycosylation and azidation reaction. At the same time, propargylated MTS derivatives using L-phenylalaninol, L-tyrosine methyl ester hydrochloride, benzoic acid and its derivatives as the starting materials were prepared by acylation, hydrolysis, alkylation, condensation reactions and so on. Then compounds 15a—15f with a 1,2,3-triazole unit were obtained from “click” chemistry reaction using copper(Ⅰ) catalyst in high yield(over 85%), which were deacetylated in the 0.41 mol/L solution of sodium methoxide to give target compounds. The structures of target compounds were confirmed by ¹H NMR, ¹³C NMR, ¹H-¹H COSY, HMQC, DEPT and ESI-MS. The anti-HBV activities of target compounds were evaluated in HepG2 2.2.15 cells. The screening results showed that all target compounds had inhibitory effect on HBV DNA replication in HepG2 2.2.15 cells. Compound 15f showed inhibition rate anti-HBV activity of 83% at 50 μg/mL and could be worthy of further research.

Key words: Hepatic targeting, Galactose, Derivatives of Matijin-Su, “Click”, chemistry, Anti-hepatitis B virus activity

中图分类号:

O629

TrendMD:

袁洁, 刘青川, 徐广灿, 梁光义, 徐必学. 基于点击化学反应的半乳糖糖基化马蹄金素衍生物的合成及抗HBV活性. 高等学校化学学报, 2016, 37(7): 1307.

YUAN Jie, LIU Qingchuan, XU Guangcan, LIANG Guangyi, XU Bixue. Synthesis and Anti-HBV Activity Evaluation of the Galactopyranosyl Derivatives of MTS Based on Click Reaction^†. Chem. J. Chinese Universities, 2016, 37(7): 1307.

图/表 9

Fig.1 Chemical structure of MTS(A) and general stucture of hepatic targeting MTS derivatives(B)

Scheme 1 Synthetic routes of target compounds 15a—15f(1) Ac2O, CH3COONa, 140 ℃; (2) TsCl, pyridine, r. t.; (3) 0.4 nm MS, BF3·Et2O, CH2Cl2, 0 ℃ to r. t.; (4) NaN3, TBAI, DMF, 60 ℃; (5) (a)(Boc)2O, DMF/H2O, r. t.; (b) propargyl bromide(80%, solution in toluene), NaH(60%, dispersion in mineral oil), DMF, 0 ℃ to r. t.; (6) TFA, CH2Cl2, 0 ℃ to r. t.; (7) benzoic acid, 4-nitrobenzoic acid or furoic acid, IBCF, NMM, CH2Cl2/DMF, 0 ℃ to r. t.; (8) 1.0 mol/L NaOH(aq.), DMF, r. t.; (9) IBCF, NMM, CH2Cl2/DMF, 0 ℃ to r. t.; (10) CH3(CH2)5Br, CH3(CH2)4Br, CH3(CH2)3I, CH3(CH2)2I, Br(CH2)3OH or allyl bromide, K2CO3, DMF, r. t.; (11) (+)-sodium L-ascorbate, CuI, DIPEA, DMF/H2O, r. t.; (12) CH3ONa, CH3OH/CH2Cl2, r. t..

Table 1 Appearance, yields, melting points, specific rotation and ESI-MS data for all intermediates*

Compd.	Appearance	Yield(%)	m. p./℃	[α $] D 20$ /(°)(c 0.5, CH₃OH)	ESI-MS, m/z
3	Pale oil	72
4	Pale oil	73			657.0 [M+Na]⁺
5	Pale oil	94			544.2 [M+K]⁺
8	Pale oil	37
12a	White solid	27	160—162	-61.0
12b	Yellow solid	29	200—202	-104.3
12c	White solid	25	98—100	-24.4
13a	White solid	83	167—169	-51.9
13b	White solid	80	135—137	-29.8
13c	Yellow solid	90	232—234	-22.6
13d	Yellow solid	88	219—221	-35.2
13e	White solid	87	123—125	-50.6
13f	White solid	84	124—126	-35.4
14a	Pale oil	93		-29.1	1024.2 [M+Na]⁺
14b	Pale oil	90		-29.0	1042.3 [M+Na]⁺
14c	Pale oil	87		-24.0	1071.2 [M+Na]⁺
14d	Pale oil	92		-31.6	1063.3 [M+H]⁺
14e	Pale oil	88		-32.9	1022.3 [M+H]⁺
14f	Pale oil	86		-35.9	1058.3 [M+Na]⁺

Table 1 Appearance, yields, melting points, specific rotation and ESI-MS data for all intermediates*

Compd.	Appearance	Yield(%)	m. p./℃	[α $] D 20$ /(°)(c 0.5, CH₃OH)	ESI-MS, m/z
3	Pale oil	72
4	Pale oil	73			657.0 [M+Na]⁺
5	Pale oil	94			544.2 [M+K]⁺
8	Pale oil	37
12a	White solid	27	160—162	-61.0
12b	Yellow solid	29	200—202	-104.3
12c	White solid	25	98—100	-24.4
13a	White solid	83	167—169	-51.9
13b	White solid	80	135—137	-29.8
13c	Yellow solid	90	232—234	-22.6
13d	Yellow solid	88	219—221	-35.2
13e	White solid	87	123—125	-50.6
13f	White solid	84	124—126	-35.4
14a	Pale oil	93		-29.1	1024.2 [M+Na]⁺
14b	Pale oil	90		-29.0	1042.3 [M+Na]⁺
14c	Pale oil	87		-24.0	1071.2 [M+Na]⁺
14d	Pale oil	92		-31.6	1063.3 [M+H]⁺
14e	Pale oil	88		-32.9	1022.3 [M+H]⁺
14f	Pale oil	86		-35.9	1058.3 [M+Na]⁺

Table 2 1H NMR data for intermediates 3—5 and 8*

Compd.	¹H NMR(CDCl₃), δ
3	7.80(d, J=8.3 Hz, 2H, ArH, 7.35(d, J=8.0 Hz, 2H, ArH), 4.17(t, J=4.8 Hz, 2H, CH₂OH), 3.75—3.68(m, 4H, OCH₂×2), 3.63—3.55(m, 6H, OCH₂×3), 2.45(s, 3H, CH₃)
4	7.79(d, J=8.3 Hz, 2H, ArH), 7.34(dd, J=8.6, 0.6 Hz, 2H, ArH), 5.38(dd, J=3.4, 1.0 Hz, 1H, 4d-H), 5.20(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.02(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.56(d, J=8.0 Hz, 1H, 1d-H), 4.20—4.09(m, 4H, 6d-H, OCH₂), 3.98—3.89(m, 2H, 5d-H, OCH₂), 3.73(ddd, J=11.0, 7.0, 3.9 Hz, 1H, OCH₂), 3.70—3.55(m, 8H, OCH₂×4), 2.45(s, 3H, CH₃), 2.15(s, 3H, CH₃CO), 2.05(s, 3H, CH₃CO), 2.05(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO)
5	5.39(dd, J=3.4, 1.1 Hz, 1H, 4d-H), 5.22(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.02(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.58(d, J=8.0 Hz, 1H, 1d-H), 4.22—4.10(m, 2H, 6d-H), 4.00—3.89(m, 2H, 5d-H, OCH₂), 3.76(ddd, J=11.0, 6.9, 4.0 Hz, 1H, OCH₂), 3.70—3.64(m, 8H, OCH₂×4), 3.41(t, J=5.0 Hz, 2H, CH₂N₃), 2.15(s, 3H, CH₃CO), 2.07(s, 3H, CH₃CO), 2.05(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO)
8	7.32—7.21(m, 5H, 5c-H—9c-H), 4.17(d, J=1.9 Hz, 2H, OCH₂C≡≡CH), 3.54(dd, J=9.1, 4.1 Hz, 1H, 1c-H), 3.38(dd, J=8.9, 7.1 Hz, 1H, 1'c-H), 3.29—3.25(m, 1H, 2c-H), 2.81(dd, J=13.5, 5.4 Hz, 1H, 3c-H), 2.58(dd, J=13.3, 8.3 Hz, 1H, 3'c-H), 2.43(t, J=2.4 Hz, 1H, OCH₂C≡≡CH)

Table 3 1H NMR and 13C NMR data for intermediates 12a—12c, 13a—13f and 14a—14f

Compd.	¹H NMR(400 MHz), δ^a	¹³C NMR, δ^b
12a	7.75—7.69(m, 2H, 3b-H, 7b-H), 7.52(t, J=7.4 Hz, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.23—7.04(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.69(d, J=8.4 Hz, 2H, 6a-H, 8a-H), 4.72(t, J=7.5 Hz, 1H, 2a-H), 4.20—4.13(m, 1H, 2c-H), 4.08(dd, J=8.2, 2.4 Hz, 2H, OCH₂C≡≡CH), 3.39(dd, J=9.4, 4.7 Hz, 1H, OCH₂C≡≡CH), 3.34—3.27(m, 2H, 1c-H), 3.03(dd, J=13.7, 7.1 Hz, 1H, 3a-H), 2.95—2.82(m, 2H, 3'a-H, 3c-H), 2.74(dd, J=13.6, 7.7 Hz, 1H, 3'c-H)	172.8(C1a), 169.6(C1b), 157.0(C7a), 139.1(C4c), 135.0(C2b), 132.7(C5b), 131.3(2C), 130.3(2C), 129.4(2C), 129.2(2C), 128.8(C4a), 128.2(C3b, C7b), 127.2(C7c), 116.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 76.0(OCH₂C≡≡CH), 71.0(C1c), 59.0(OCH₂·C≡≡CH), 56.6(C2a), 51.6(C2c), 38.2(C3a), 38.0(C3c)
12b	9.19(s, 1H, OH), 8.80(d, J=8.5 Hz, 1H, NHCO), 8.29(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.09(d, J=8.4 Hz, 1H, NHCO), 8.00(d, J=9.0 Hz, 2H, 3b-H, 7b-H), 7.23—7.11(m, 5H, 5c-H—9c-H), 7.08(d, J=8.5 Hz, 2H, 5a-H, 9a-H), 6.62(d, J=8.5 Hz, 2H, 6a-H, 8a-H), 4.67—4.56(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.11—4.01(m, 1H, 2c-H), 3.49—3.31(m, 3H, OCH₂C≡≡CH, 1c-H), 2.91(dd, J=13.8, 4.6 Hz, 1H, 3a-H), 2.86—2.77(m, 2H, 3'a-H, 3c-H), 2.70(dd, J=13.7, 8.2 Hz, 1H, 3'a-H)	170.8(C1a), 164.4(C1b), 155.7(C7a), 149.0(C5b), 139.7(C4c), 138.4(C2b), 130.1(2C), 129.2(2C), 129.0(2C), 128.2, 128.1(2C), 126.1(C7c), 123.4(C4b, C6b), 114.9(C6a, C8a), 80.2(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.3(C1c), 57.7(OCH₂C≡≡CH), 55.3(C2a), 50.0(C2c), 36.6(C3a, C3c)
12c	9.19(s, 1H, OH), 8.13—8.02(m, 2H, NHCO×2), 7.81(dd, J=1.7, 0.7 Hz, 1H, 5b-H), 7.23—7.10(m, 6H, 3b-H, 5c-H—9c-H), 7.02(d, J=8.5 Hz, 2H, 5a-H, 9a-H), 6.63—6.57(m, 3H, 4b-H, 6a-H, 8a-H), 4.59—4.49(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.08—3.99(m, 1H, 2c-H), 3.48—3.33(m, 3H, OCH₂C≡≡CH, 1c-H), 2.89—2.76(m, 3H, 3a-H, 3c-H), 2.69(dd, J=13.7, 8.1 Hz, 1H, 3'c-H)	170.8(C1a), 157.3, 155.8(C1b, C7a), 147.5(C2b), 145.1(C5b), 138.4(C4c), 130.1(2C), 129.2(2C), 128.1(2C), 128.0, 126.1(C7c), 114.9(C6a, C8a), 113.7, 111.9(C3b, C4b), 80.2(OCH₂C≡≡CH), 77.4(OCH₂·C≡≡CH), 70.3(C1c), 57.7(OCH₂C≡≡CH), 54.2(C2a), 50.0(C2c), 36.7(C3a, C3c)
13a	8.42(d, J=8.5 Hz, 1H, NHCO), 8.04(d, J=8.4 Hz, 1H, NHCO), 7.80—7.75(m, 2H, 3b-H, 7b-H), 7.54—7.40(m, 3H, 4b-H—6b-H), 7.27—7.07(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.81(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.04—5.94(m, 1H, OCH₂CH CH₂), 5.39—5.30(m, 1H, OCH₂CH CH), 5.23—5.18(m, 1H, OCH₂·CH CH), 4.66—4.56(m, 1H, 2a-H), 4.47(dt, J=5.2, 1.4 Hz, 2H, OCH₂CH CH₂), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.09—4.03(m, 1H, 2c-H), 3.66—3.24(m, 3H, OCH₂C≡≡CH, 1c-H), 2.97—2.78(m, 3H, 3a-H, 3c-H), 2.74—2.67(m, 1H, 3'c-H)	171.3(C1a), 166.5(C1b), 156.9(C7a), 138.6(C4c), 134.2(C2b), 134.0(OCH₂·CH CH₂), 131.6(C5b), 130.4(2C), 130.4(C4a), 129.4(2C), 128.5(2C), 128.4(2C), 127.6(C3b, C7b), 126.3(C7c), 117.6(OCH₂CH CH₂), 114.4(C6a, C8a), 80.4(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.6(C1c), 68.3(OCH₂CH CH₂), 57.9(OCH₂·C≡≡CH), 55.2(C2a), 50.2(C2c), 36.9(C3a), 36.7(C3c)
13b	8.41(d, J=8.5 Hz, 1H, NHCO), 8.04(d, J=8.4 Hz, 1H, NHCO), 7.81—7.74(m, 2H, H-3b, 7b-H), 7.54—7.41(m, 3H, 4b-H—6b-H), 7.31—7.02(m, 7H, H-5a, 9a-H, 5c-H—9c-H), 6.79(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.71—4.54(m, 1H, 2a-H), 4.13(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—4.01(m, 1H, 2c-H), 3.94(t, J=6.4 Hz, 2H, OCH₂CH₂CH₂OH), 3.70—3.24(m, 5H, OCH₂CH₂CH₂OH, OCH₂C≡≡CH, 1c-H), 2.97—2.76(m, 3H, 3a-H, 3c-H), 2.74—2.66(m, 1H, 3'c-H), 1.86—1.75(m, 2H, OCH₂CH₂CH₂OH)	171.2(C1a), 166.3(C1b), 157.3(C7a), 138.5(C4c), 134.2(C2b), 131.4(C5b), 130.3(2C), 130.1(C4a), 129.3(2C), 128.3(2C), 128.3(2C), 127.5(C3b, C7b), 126.2(C7c), 114.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.5(C1c), 64.5(OCH₂·CH₂CH₂OH), 58.6(OCH₂CH₂CH₂OH), 57.8(OCH₂C≡≡ CH), 55.2(C2a), 50.1(C2c), 36.7(C3a), 36.6(C3c), 32.2(OCH₂CH₂CH₂OH)
13c	8.83(d, J=8.2 Hz, 1H, NHCO), 8.29(d, J=8.4 Hz, 2H, 4b-H, 6b-H), 8.12(d, J=8.0 Hz, 1H, NHCO), 8.00(d, J=8.2 Hz, 2H, 3b-H, 7b-H), 7.29—7.09(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.0 Hz, 2H, 6a-H, 8a-H), 4.70—4.59(m, 1H, 2a-H), 4.17—4.02(m, 3H, OCH₂C≡≡CH, 2c-H), 3.83(t, J=5.8 Hz, 2H, OCH₂CH₂CH₃), 3.61—3.24(m, 3H, OCH₂C≡≡CH, 1c-H), 3.03—2.76(m, 3H, 3a-H, 3c-H), 2.76—2.66(m, 1H, 3'c-H), 1.76—1.59(m, 2H, OCH₂CH₂CH₃), 0.93(t, J=7.1 Hz, 3H, OCH₂CH₂CH₃)	170.9(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 139.8(C4c), 138.5(C2b), 130.3(2C), 130.0(C4a), 129.3(2C), 129.0(C3b, C7b), 128.3(2C), 126.2(C7c), 123.6(C4b, C6b), 114.1(C6a, C8a), 80.3(OCH₂·C≡≡CH), 77.4(OCH₂C≡≡CH), 70.4(C1c), 69.0(OCH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 55.4(C2a), 50.1(C2c), 36.7(C3a), 36.7(C3c), 22.2(OCH₂CH₂CH₃), 10.6(OCH₂CH₂CH₃)
13d	8.83(d, J=8.5 Hz, 1H, NHCO), 8.29(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.12(d, J=8.4 Hz, 1H, NHCO), 8.00(d, J=8.9 Hz, 2H, H-3b, 7b-H), 7.25—7.10(m, 7H, 5a-H, 9a-H, 5c-H—9c-H),	170.8(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 140.0(C4c), 138.5(C2b), 130.3(2C), 129.8(C4a), 129.3(2C), 129.0(2C),
13d	6.79(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.68—4.60(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.10—4.03(m, 1H, 2c-H), 3.87(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₃), 3.55—3.27(m, 3H, OCH₂C≡≡CH, 1c-H), 3.00—2.79(m, 3H, 3a-H, 3c-H), 2.75—2.67(m, 1H, 3'c-H), 1.68—1.58(m, 2H, OCH₂CH₂·CH₂CH₃), 1.45—1.32(m, 2H, OCH₂CH₂CH₂CH₃), 0.89(t, J=7.4 Hz, 3H, OCH₂CH₂CH₂CH₃)	128.2(2C), 126.2(C7c), 123.5(C4b, C6b), 114.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 77.3(OCH₂C≡≡CH), 70.4(C1c), 67.0(OCH₂·CH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 55.3(C2a), 50.0(C2c), 36.7(C3a), 36.6(C3c), 30.9(OCH₂CH₂CH₂CH₃), 18.8(OCH₂CH₂·CH₂CH₃), 13.8(OCH₂CH₂CH₂CH₃)
13e	8.14(d, J=8.6 Hz, 1H, NHCO), 8.09(d, J=8.4 Hz, 1H, NHCO), 7.80(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.22—7.08(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.60(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.60—4.52(m, 1H, 2a-H), 4.12(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—4.00(m, 1H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₂CH₃), 3.59—3.31(m, 3H, OCH₂C≡≡CH, 1c-H), 2.92—2.76(m, 3H, 3a-H, 3c-H), 2.73—2.64(m, 1H, 3'c-H), 1.70—1.61(m, 2H, OCH₂·CH₂CH₂CH₂CH₃), 1.41—1.25(m, 4H, OCH₂CH₂CH₂CH₂CH₃), 0.86(t, J=7.1 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	170.9(C1a), 157.5, 157.4(C1b, C7a), 147.5(C2b), 145.3(C5b), 138.5(C4c), 130.3(2C), 129.7(C4a), 129.4(2C), 128.3(2C), 126.3(C7c), 114.1(C6a, C8a), 114.0, 112.1(C3b, C4b), 80.3(OCH₂C≡≡CH), 77.5(OCH₂C≡≡CH), 70.5(C1c), 67.4(OCH₂·CH₂CH₂CH₂CH₃), 57.9(OCH₂C≡≡CH), 54.3(C2a), 50.1(C2c), 36.8(C3a), 36.7(C3c), 28.6(OCH₂CH₂CH₂CH₂CH₃), 27.9(OCH₂·CH₂CH₂CH₂CH₃), 22.1(OCH₂CH₂CH₂CH₂·CH₃), 14.1(OCH₂CH₂CH₂CH₂CH₃)
13f	8.14(d, J=8.5 Hz, 1H, NHCO), 8.09(d, J=8.4 Hz, 1H, NHCO), 7.81(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.29—7.05(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.60(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.61—4.52(m, 1H, 2a-H), 4.13(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—3.99(m, 1H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 3.61—3.27(m, 3H, OCH₂C≡≡CH, 1c-H), 2.94—2.76(m, 3H, 3a-H, 3c-H), 2.74—2.63(m, 1H, 3'c-H), 1.71—1.58(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.42—1.32(m, 2H, OCH₂CH₂CH₂·CH₂CH₂CH₃), 1.32—1.21(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.85(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₂CH₃)	170.8(C1a), 157.5, 157.3(C1b, C7a), 147.5(C2b), 145.3(C5b), 138.5(C4c), 130.3(2C), 129.6(C4a), 129.3(2C), 128.3(2C), 126.2(C7c), 114.1(C6a, C8a), 113.9, 112.0,(C3b, C4b), 80.3(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.4(C1c), 67.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 54.2(C2a), 50.1(C2c), 36.7(C3a), 36.7(C3c), 31.1(OCH₂CH₂CH₂CH₂CH₂CH₃),28.8(OCH₂CH₂CH₂CH₂CH₂CH₃), 25.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 22.2(OCH₂CH₂CH₂·CH₂CH₂CH₃), 14.1(OCH₂CH₂CH₂CH₂·CH₂CH₃)
14a	7.72(d, J=7.7 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.51(t, J=7.2 Hz, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.22—7.05(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.88(d, J=7.5 Hz, 1H, NHCO), 6.82(d, J=8.3 Hz, 2H, 6a-H, 8a-H), 6.40(d, J=8.4 Hz, 1H, NHCO), 6.03(ddd, J=22.0, 10.5, 5.2 Hz, 1H, OCH₂CH CH₂), 5.44—5.34(m, 2H, 4d-H, OCH₂CH CH), 5.29—5.17(m, 2H, 2d-H, OCH₂CH CH), 5.03(dd, J=10.4, 3.2 Hz, 1H, 3d-H), 4.76(dd, J=13.6, 7.2 Hz, 1H, 2a-H), 4.59—4.45(m, 7H, H-1d, OCH₂CH₂—N—N, OCH₂C CH, OCH₂CH CH₂), 4.26—4.07(m, 3H, 2c-H, 6d-H), 3.99—3.83(m, 4H, 5d-H, OCH₂×2), 3.74—3.67(m, 1H, OCH₂), 3.65—3.55(m, 6H, OCH₂×3), 3.40(dd, J=9.2, 3.0 Hz, 1H, 1c-H), 3.25(dd, J=9.2, 3.8 Hz, 1H, 1'c-H), 3.14(dd, J=13.8, 5.7 Hz, 1H, 3a-H), 3.03(dd, J=13.7, 7.8 Hz, 1H, 3'a-H), 2.78(d, J=5.9 Hz, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.98(s, 3H, CH₃CO)	170.6, 170.4, 170.3, 170.2, 170.0(C1a, CH₃CO×4), 167.0(C1b), 157.7(C7a), 144.6(OCH₂C CH), 137.7(C4c), 133.9(C2b), 133.3(OCH₂CH CH₂), 131.9(C5b), 130.5(2C), 129.4(2C), 128.9(C4a), 128.7(C4b, C6b), 128.5(2C), 127.2(C3b, C7b), 126.5(C7c), 123.8(OCH₂C CH), 117.9(OCH₂CH CH₂), 114.9(C6a, C8a), 101.4(C1d), 71.0(C3d), 70.71, 70.69, 70.6, 70.3(C5d, OCH₂×3), 70.0(C1c), 69.6, 69.2(OCH₂×2), 68.9, 68.8(C2d, OCH₂CH CH₂), 67.1(C4d), 64.6(OCH₂·C CH), 61.3(C6d), 55.0(C2a), 50.6(C2c), 50.3(OCH₂CH₂—N—N), 37.8(C3a), 37.4(C3c), 20.9, 20.82, 20.80, 20.7,(CH₃CO×4)
Compd.	¹H NMR(400 MHz), δ^a	¹³C NMR, δ^b
14b	7.77—7.74(m, 2H, 3b-H, 7b-H), 7.65(s, 1H, OCH₂C CH), 7.54—7.49(m, 1H, 5b-H), 7.46—7.41(m, 2H, 4b-H, 6b-H), 7.20—7.06(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.95(d, J=7.7 Hz, 1H, NHCO), 6.81(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.20(d, J=8.6 Hz, 1H, NHCO), 5.39(dd, J=3.4, 1.0 Hz, 1H, 4d-H), 5.20(dd, J=10.5, 7.9 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.76—4.70(m, 1H, 2a-H), 4.58—4.41(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.21—4.05(m, 5H, 6d-H, 2c-H, OCH₂CH₂CH₂OH), 3.98—3.86(m, 4H, 5d-H, OCH₂×2), 3.83(t, J=5.7 Hz, 2H, OCH₂CH₂CH₂OH), 3.70(ddd, J=10.8, 6.2, 4.4 Hz, 1H, OCH₂), 3.63—3.58(m, 6H, OCH₂×3), 3.33(dd, J=9.3, 3.2 Hz, 1H, 1c-H), 3.17(dd, J=13.5, 5.4 Hz, 1H, 1'c-H), 3.09(dd, J=9.3, 3.9 Hz, 1H, 3a-H), 2.95(dd, J=13.5, 8.9 Hz, 1H, 3'a-H), 2.83—2.70(m, 2H, 3c-H), 2.13(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.05—1.99(m, 2H, OCH₂CH₂CH₂OH), 1.98(s, 3H, CH₃CO)	170.6, 170.4, 170.3, 170.1, 169.6(C1a, CH₃CO×4), 166.9(C1b), 158.0(C7a), 144.7(OCH₂C CH), 137.7(C4c), 134.0(C2b), 131.9(C5b), 130.5(2C), 129.4(2C), 128.8(C4a), 128.7(C4b, C6b), 128.5(2C), 127.2(C3b, C7b), 126.6(C7c), 123.7(OCH₂C CH), 114.6(C6a, C8a), 101.4(C1d), 71.0(C3d), 70.7, 70.7, 70.6, 70.3(C5d, OCH₂×3), 69.8(C1c), 69.5, 69.2(OCH₂×2), 68.9(C2d), 67.1(C4d), 65.2(OCH₂CH₂CH₂OH), 64.7(OCH₂C CH), 61.3(C6d), 59.5(OCH₂CH₂CH₂OH), 55.4(C2a), 50.40(C2c, OCH₂CH₂—N—N), 38.3(C3a), 37.4(C3c), 32.2(OCH₂CH₂CH₂OH), 20.9, 20.8, 20.7(CH₃CO×4)
14c	8.27(d, J=8.8 Hz, 2H, 4b-H, 6b-H), 7.90(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.23—7.08(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.80(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.40(d, J=8.4 Hz, 1H, NHCO), 5.39(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.21(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.79—4.72(m, 1H, 2a-H), 4.59—4.50(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.06(m, 3H, 6d-H, 2c-H), 4.01—3.81(m, 6H, 5d-H, OCH₂×3), 3.71(ddd, J=10.7, 6.1, 4.4 Hz, 1H, OCH₂), 3.64—3.56(m, 6H, OCH₂×3), 3.43(dd, J=9.5, 3.6 Hz, 1H, 1c-H), 3.27(dd, J=9.4, 3.9 Hz, 1H, 1'c-H), 3.15(dd, J=13.8, 5.6 Hz, 1H, 3a-H), 3.03(dd, J=13.8, 7.9 Hz, 1H, 3'a-H), 2.86—2.72(m, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.83—1.73(m, 2H, OCH₂CH₂CH₃), 1.01(t, J=7.4 Hz, 3H, OCH₂CH₂CH₃)	170.6, 170.4, 170.3, 169.9, 169.6(C1a, CH₃CO×4), 164.9(C1b), 158.4(C7a), 149.8(C5b), 144.5(OCH₂C CH), 139.7(C4c), 137.7(C2b), 130.5(2C), 129.4(2C), 128.5(2C), 128.4(C3b, C7b), 128.1(C4a), 126.6(C7c), 123.9(C4b, C6b), 123.8(OCH₂·C CH), 114.7(C6a, C8a), 101.5(C1d), 71.0(C3d), 70.8, 70.7, 70.7, 70.3(C5d, OCH₂×3), 69.9(C1c), 69.6, 69.3(OCH₂×3), 68.9(C2d), 67.1(C4d), 64.5(OCH₂·C CH), 61.3(C6d), 55.3(C2a), 50.9(C2c), 50.4(OCH₂CH₂—N—N), 38.0(C3a), 37.4(C3c), 22.7(OCH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃CO×4), 10.7(OCH₂CH₂CH₃)
14d	8.27(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 7.90(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.22—7.08(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.42(d, J=8.4 Hz, 1H, NHCO), 5.39(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.21(dd, J=10.5, 7.9 Hz, 1H, 2d-H), 5.04(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.80—4.72(m, 1H, 2a-H), 4.59—4.48(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.24—4.06(m, 3H, 6d-H, 2c-H), 4.03—3.83(m, 6H, 5d-H, OCH₂×3), 3.71(ddd, J=10.7, 6.1, 4.5 Hz, 1H, OCH₂), 3.65—3.54(m, 6H, OCH₂×3), 3.43(dd, J=9.5, 3.6 Hz, 1H, 1c-H), 3.27(dd, J=9.5, 3.9 Hz, 1H, 1'c-H), 3.14(dd, J=13.8, 5.6 Hz, 1H, 3a-H), 3.03(dd, J=13.8, 7.8 Hz, 1H, 3'a-H), 2.87—2.73(m, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.78—1.69(m, 2H, OCH₂CH₂CH₂CH₃), 1.53—1.40(m, 2H, OCH₂CH₂CH₂CH₃), 0.96(t, J=7.4 Hz, 3H, OCH₂CH₂·CH₂CH₃)	170.6, 170.4, 170.3, 169.9, 169.6(C1a, CH₃CO×4), 164.9(C1b), 158.4(C7a), 149.8(C5b), 144.5(OCH₂C CH), 139.7(C4c), 137.7(C2b), 130.5(2C), 129.4(2C), 128.5(2C), 128.4(C3b, C7b), 128.1(C4a), 126.6(C7c), 123.9(C4b, C6b), 123.8(OCH₂·C CH), 114.7(C6a, C8a), 101.5(C1d), 71.0(C3d), 70.8, 70.7, 70.3(C5d, OCH₂×3), 69.9(C1c), 69.6, 69.3(OCH₂×2), 68.9(C2d), 67.8(OCH₂), 67.1(C4d), 64.5(OCH₂C CH), 61.3(C6d), 55.3(C2a), 50.9(C2c), 50.4(OCH₂CH₂—N—N), 38.0(C3a), 37.4(C3c), 31.4(OCH₂CH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃CO×4), 19.4(OCH₂·CH₂CH₂CH₃), 14.0(OCH₂CH₂CH₂CH₃)
14e	7.68(s, 1H, OCH₂C CH), 7.46(d, J=0.9 Hz, 1H, 5b-H), 7.22—7.02(m, 8H, 5a-H, 9a-H, 3b-H, 5c-H—9c-H), 6.94(d, J=8.0 Hz, 1H, NHCO), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.51(dd, J=3.4, 1.7 Hz, 1H, 4b-H), 6.34(d, J=8.6 Hz, 1H, NHCO), 5.39(d, J=3.0 Hz, 1H, 4d-H), 5.21(dd, J=10.4, 8.0 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.71(dd, J=14.0, 7.7 Hz, 1H, 2a-H), 4.59—4.51(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.08(m, 3H, 6d-H, 2c-H), 4.00—3.84(m, 6H, 5d-H, OCH₂×3), 3.74—3.67(m, 1H, OCH₂), 3.65—3.55(m, 6H, OCH₂×3), 3.37(dd, J=9.4, 3.4 Hz, 1H, 1c-H), 3.22(dd, J=9.4, 4.2 Hz, 1H, 1'c-H), 3.10(dd, J=13.8, 6.0 Hz, 1H, 3a-H), 2.99(dd, J=13.8, 7.8 Hz, 1H, 3'a-H), 2.77(dd, J=7.2, 2.9 Hz, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.79—1.69(m, 2H, OCH₂CH₂CH₂CH₂CH₃), 1.47—1.30(m, 4H, OCH₂CH₂CH₂·CH₂CH₃), 0.91(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	170.4, 170.2, 170.2, 169.8, 169.4(C1a, CH₃CO×4), 158.0, 157.8(C1b, C7a), 147.3(C2b), 144.4, 144.2(C5b, OCH₂C CH), 137.5(C4c), 130.3(2C), 129.3(2C), 128.3(2C), 128.1(C4a), 126.3(C7c), 123.6(OCH₂C CH), 114.6(C3b), 114.5(C6a, C8a), 112.1(C4b), 101.2(C1d), 70.8(C3d), 70.5, 70.1(C5d, OCH₂×3), 69.7(C1c), 69.4, 69.1(OCH₂×2), 68.7(C2d), 67.8(OCH₂), 66.9(C4d), 64.4(OCH₂C CH), 61.2(C6d), 54.2(C2a), 50.3, 50.2(C2c, OCH₂·CH₂—N—N), 37.6(C3a), 37.2(C3c), 28.9(OCH₂CH₂CH₂CH₂CH₃), 28.1(OCH₂·CH₂CH₂CH₂CH₃), 22.4(OCH₂CH₂CH₂·CH₂CH₃), 20.8, 20.7, 20.6(CH₃CO×4), 14.0(OCH₂CH₂CH₂CH₂CH₃)
14f	7.67(s, 1H, OCH₂C CH), 7.45(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.19—7.04(m, 8H, 5a-H, 9a-H, 3b-H, 5c-H—9c-H), 6.92(d, J=8.0 Hz, 1H, NHCO), 6.78(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.50(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 6.30(d, J=8.6 Hz, 1H, NHCO), 5.38(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.20(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.02(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.74—4.66(m, 1H, 2a-H), 4.60—4.49(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.07(m, 3H, 6d-H, 2c-H), 3.99—3.85(m, 6H, 5d-H, OCH₂×3), 3.70(ddd, J=10.8, 6.2, 4.5 Hz, 1H, OCH₂), 3.63—3.55(m, 6H, OCH₂×3), 3.37(dd, J=9.4, 3.5 Hz, 1H, 1c-H), 3.22(dd, J=9.4, 4.2 Hz, 1H, 1'c-H), 3.09(dd, J=13.8, 6.0 Hz, 1H, 3a-H), 2.99(dd, J=13.8, 7.7 Hz, 1H, 3'a-H), 2.76(dd, J=7.2, 2.2 Hz, 2H, 3c-H), 2.13(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.98(s, 3H, CH₃CO), 1.77—1.69(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.47—1.37(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.35—1.27(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.88(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₂CH₃)	170.5, 170.4, 170.3, 170.0, 169.6(C1a, CH₃CO×4), 158.2, 158.0(C1b, C7a), 147.5(C2b), 144.6, 144.4(C5b, OCH₂C CH), 137.7(C4c), 130.4(2C), 129.4(2C), 128.4(2C), 128.3(C4a), 126.5(C7c), 123.8(OCH₂C CH), 114.8(C3b), 114.7(C6a, C8a), 112.2(C4b), 101.4(C1d), 71.0(C3d), 70.7, 70.6, 70.3(C5d, OCH₂×3), 69.9 (C1c), 69.6, 69.2(OCH₂×2), 68.9(C2d), 68.0(OCH₂), 67.1(C4d), 64.5(OCH₂C CH), 61.3(C6d), 54.3(C2a), 50.5, 50.3(C2c, OCH₂CH₂—N—N), 37.7(C3a), 37.3(C3c), 31.7(OCH₂CH₂CH₂CH₂CH₂CH₃), 29.3(OCH₂CH₂CH₂CH₂CH₂CH₃), 25.8(OCH₂·CH₂CH₂CH₂CH₂CH₃), 22.7(OCH₂CH₂·CH₂CH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃·CO×4), 14.2(OCH₂CH₂CH₂CH₂CH₂CH₃)

Table 3 1H NMR and 13C NMR data for intermediates 12a—12c, 13a—13f and 14a—14f

Compd.	¹H NMR(400 MHz), δ^a	¹³C NMR, δ^b
12a	7.75—7.69(m, 2H, 3b-H, 7b-H), 7.52(t, J=7.4 Hz, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.23—7.04(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.69(d, J=8.4 Hz, 2H, 6a-H, 8a-H), 4.72(t, J=7.5 Hz, 1H, 2a-H), 4.20—4.13(m, 1H, 2c-H), 4.08(dd, J=8.2, 2.4 Hz, 2H, OCH₂C≡≡CH), 3.39(dd, J=9.4, 4.7 Hz, 1H, OCH₂C≡≡CH), 3.34—3.27(m, 2H, 1c-H), 3.03(dd, J=13.7, 7.1 Hz, 1H, 3a-H), 2.95—2.82(m, 2H, 3'a-H, 3c-H), 2.74(dd, J=13.6, 7.7 Hz, 1H, 3'c-H)	172.8(C1a), 169.6(C1b), 157.0(C7a), 139.1(C4c), 135.0(C2b), 132.7(C5b), 131.3(2C), 130.3(2C), 129.4(2C), 129.2(2C), 128.8(C4a), 128.2(C3b, C7b), 127.2(C7c), 116.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 76.0(OCH₂C≡≡CH), 71.0(C1c), 59.0(OCH₂·C≡≡CH), 56.6(C2a), 51.6(C2c), 38.2(C3a), 38.0(C3c)
12b	9.19(s, 1H, OH), 8.80(d, J=8.5 Hz, 1H, NHCO), 8.29(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.09(d, J=8.4 Hz, 1H, NHCO), 8.00(d, J=9.0 Hz, 2H, 3b-H, 7b-H), 7.23—7.11(m, 5H, 5c-H—9c-H), 7.08(d, J=8.5 Hz, 2H, 5a-H, 9a-H), 6.62(d, J=8.5 Hz, 2H, 6a-H, 8a-H), 4.67—4.56(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.11—4.01(m, 1H, 2c-H), 3.49—3.31(m, 3H, OCH₂C≡≡CH, 1c-H), 2.91(dd, J=13.8, 4.6 Hz, 1H, 3a-H), 2.86—2.77(m, 2H, 3'a-H, 3c-H), 2.70(dd, J=13.7, 8.2 Hz, 1H, 3'a-H)	170.8(C1a), 164.4(C1b), 155.7(C7a), 149.0(C5b), 139.7(C4c), 138.4(C2b), 130.1(2C), 129.2(2C), 129.0(2C), 128.2, 128.1(2C), 126.1(C7c), 123.4(C4b, C6b), 114.9(C6a, C8a), 80.2(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.3(C1c), 57.7(OCH₂C≡≡CH), 55.3(C2a), 50.0(C2c), 36.6(C3a, C3c)
12c	9.19(s, 1H, OH), 8.13—8.02(m, 2H, NHCO×2), 7.81(dd, J=1.7, 0.7 Hz, 1H, 5b-H), 7.23—7.10(m, 6H, 3b-H, 5c-H—9c-H), 7.02(d, J=8.5 Hz, 2H, 5a-H, 9a-H), 6.63—6.57(m, 3H, 4b-H, 6a-H, 8a-H), 4.59—4.49(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.08—3.99(m, 1H, 2c-H), 3.48—3.33(m, 3H, OCH₂C≡≡CH, 1c-H), 2.89—2.76(m, 3H, 3a-H, 3c-H), 2.69(dd, J=13.7, 8.1 Hz, 1H, 3'c-H)	170.8(C1a), 157.3, 155.8(C1b, C7a), 147.5(C2b), 145.1(C5b), 138.4(C4c), 130.1(2C), 129.2(2C), 128.1(2C), 128.0, 126.1(C7c), 114.9(C6a, C8a), 113.7, 111.9(C3b, C4b), 80.2(OCH₂C≡≡CH), 77.4(OCH₂·C≡≡CH), 70.3(C1c), 57.7(OCH₂C≡≡CH), 54.2(C2a), 50.0(C2c), 36.7(C3a, C3c)
13a	8.42(d, J=8.5 Hz, 1H, NHCO), 8.04(d, J=8.4 Hz, 1H, NHCO), 7.80—7.75(m, 2H, 3b-H, 7b-H), 7.54—7.40(m, 3H, 4b-H—6b-H), 7.27—7.07(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.81(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.04—5.94(m, 1H, OCH₂CH CH₂), 5.39—5.30(m, 1H, OCH₂CH CH), 5.23—5.18(m, 1H, OCH₂·CH CH), 4.66—4.56(m, 1H, 2a-H), 4.47(dt, J=5.2, 1.4 Hz, 2H, OCH₂CH CH₂), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.09—4.03(m, 1H, 2c-H), 3.66—3.24(m, 3H, OCH₂C≡≡CH, 1c-H), 2.97—2.78(m, 3H, 3a-H, 3c-H), 2.74—2.67(m, 1H, 3'c-H)	171.3(C1a), 166.5(C1b), 156.9(C7a), 138.6(C4c), 134.2(C2b), 134.0(OCH₂·CH CH₂), 131.6(C5b), 130.4(2C), 130.4(C4a), 129.4(2C), 128.5(2C), 128.4(2C), 127.6(C3b, C7b), 126.3(C7c), 117.6(OCH₂CH CH₂), 114.4(C6a, C8a), 80.4(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.6(C1c), 68.3(OCH₂CH CH₂), 57.9(OCH₂·C≡≡CH), 55.2(C2a), 50.2(C2c), 36.9(C3a), 36.7(C3c)
13b	8.41(d, J=8.5 Hz, 1H, NHCO), 8.04(d, J=8.4 Hz, 1H, NHCO), 7.81—7.74(m, 2H, H-3b, 7b-H), 7.54—7.41(m, 3H, 4b-H—6b-H), 7.31—7.02(m, 7H, H-5a, 9a-H, 5c-H—9c-H), 6.79(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.71—4.54(m, 1H, 2a-H), 4.13(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—4.01(m, 1H, 2c-H), 3.94(t, J=6.4 Hz, 2H, OCH₂CH₂CH₂OH), 3.70—3.24(m, 5H, OCH₂CH₂CH₂OH, OCH₂C≡≡CH, 1c-H), 2.97—2.76(m, 3H, 3a-H, 3c-H), 2.74—2.66(m, 1H, 3'c-H), 1.86—1.75(m, 2H, OCH₂CH₂CH₂OH)	171.2(C1a), 166.3(C1b), 157.3(C7a), 138.5(C4c), 134.2(C2b), 131.4(C5b), 130.3(2C), 130.1(C4a), 129.3(2C), 128.3(2C), 128.3(2C), 127.5(C3b, C7b), 126.2(C7c), 114.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.5(C1c), 64.5(OCH₂·CH₂CH₂OH), 58.6(OCH₂CH₂CH₂OH), 57.8(OCH₂C≡≡ CH), 55.2(C2a), 50.1(C2c), 36.7(C3a), 36.6(C3c), 32.2(OCH₂CH₂CH₂OH)
13c	8.83(d, J=8.2 Hz, 1H, NHCO), 8.29(d, J=8.4 Hz, 2H, 4b-H, 6b-H), 8.12(d, J=8.0 Hz, 1H, NHCO), 8.00(d, J=8.2 Hz, 2H, 3b-H, 7b-H), 7.29—7.09(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.0 Hz, 2H, 6a-H, 8a-H), 4.70—4.59(m, 1H, 2a-H), 4.17—4.02(m, 3H, OCH₂C≡≡CH, 2c-H), 3.83(t, J=5.8 Hz, 2H, OCH₂CH₂CH₃), 3.61—3.24(m, 3H, OCH₂C≡≡CH, 1c-H), 3.03—2.76(m, 3H, 3a-H, 3c-H), 2.76—2.66(m, 1H, 3'c-H), 1.76—1.59(m, 2H, OCH₂CH₂CH₃), 0.93(t, J=7.1 Hz, 3H, OCH₂CH₂CH₃)	170.9(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 139.8(C4c), 138.5(C2b), 130.3(2C), 130.0(C4a), 129.3(2C), 129.0(C3b, C7b), 128.3(2C), 126.2(C7c), 123.6(C4b, C6b), 114.1(C6a, C8a), 80.3(OCH₂·C≡≡CH), 77.4(OCH₂C≡≡CH), 70.4(C1c), 69.0(OCH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 55.4(C2a), 50.1(C2c), 36.7(C3a), 36.7(C3c), 22.2(OCH₂CH₂CH₃), 10.6(OCH₂CH₂CH₃)
13d	8.83(d, J=8.5 Hz, 1H, NHCO), 8.29(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.12(d, J=8.4 Hz, 1H, NHCO), 8.00(d, J=8.9 Hz, 2H, H-3b, 7b-H), 7.25—7.10(m, 7H, 5a-H, 9a-H, 5c-H—9c-H),	170.8(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 140.0(C4c), 138.5(C2b), 130.3(2C), 129.8(C4a), 129.3(2C), 129.0(2C),
13d	6.79(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.68—4.60(m, 1H, 2a-H), 4.13(d, J=2.4 Hz, 2H, OCH₂C≡≡CH), 4.10—4.03(m, 1H, 2c-H), 3.87(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₃), 3.55—3.27(m, 3H, OCH₂C≡≡CH, 1c-H), 3.00—2.79(m, 3H, 3a-H, 3c-H), 2.75—2.67(m, 1H, 3'c-H), 1.68—1.58(m, 2H, OCH₂CH₂·CH₂CH₃), 1.45—1.32(m, 2H, OCH₂CH₂CH₂CH₃), 0.89(t, J=7.4 Hz, 3H, OCH₂CH₂CH₂CH₃)	128.2(2C), 126.2(C7c), 123.5(C4b, C6b), 114.1(C6a, C8a), 80.3(OCH₂C≡≡CH), 77.3(OCH₂C≡≡CH), 70.4(C1c), 67.0(OCH₂·CH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 55.3(C2a), 50.0(C2c), 36.7(C3a), 36.6(C3c), 30.9(OCH₂CH₂CH₂CH₃), 18.8(OCH₂CH₂·CH₂CH₃), 13.8(OCH₂CH₂CH₂CH₃)
13e	8.14(d, J=8.6 Hz, 1H, NHCO), 8.09(d, J=8.4 Hz, 1H, NHCO), 7.80(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.22—7.08(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.60(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.60—4.52(m, 1H, 2a-H), 4.12(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—4.00(m, 1H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₂CH₃), 3.59—3.31(m, 3H, OCH₂C≡≡CH, 1c-H), 2.92—2.76(m, 3H, 3a-H, 3c-H), 2.73—2.64(m, 1H, 3'c-H), 1.70—1.61(m, 2H, OCH₂·CH₂CH₂CH₂CH₃), 1.41—1.25(m, 4H, OCH₂CH₂CH₂CH₂CH₃), 0.86(t, J=7.1 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	170.9(C1a), 157.5, 157.4(C1b, C7a), 147.5(C2b), 145.3(C5b), 138.5(C4c), 130.3(2C), 129.7(C4a), 129.4(2C), 128.3(2C), 126.3(C7c), 114.1(C6a, C8a), 114.0, 112.1(C3b, C4b), 80.3(OCH₂C≡≡CH), 77.5(OCH₂C≡≡CH), 70.5(C1c), 67.4(OCH₂·CH₂CH₂CH₂CH₃), 57.9(OCH₂C≡≡CH), 54.3(C2a), 50.1(C2c), 36.8(C3a), 36.7(C3c), 28.6(OCH₂CH₂CH₂CH₂CH₃), 27.9(OCH₂·CH₂CH₂CH₂CH₃), 22.1(OCH₂CH₂CH₂CH₂·CH₃), 14.1(OCH₂CH₂CH₂CH₂CH₃)
13f	8.14(d, J=8.5 Hz, 1H, NHCO), 8.09(d, J=8.4 Hz, 1H, NHCO), 7.81(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.29—7.05(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.60(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.61—4.52(m, 1H, 2a-H), 4.13(d, J=2.3 Hz, 2H, OCH₂C≡≡CH), 4.09—3.99(m, 1H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 3.61—3.27(m, 3H, OCH₂C≡≡CH, 1c-H), 2.94—2.76(m, 3H, 3a-H, 3c-H), 2.74—2.63(m, 1H, 3'c-H), 1.71—1.58(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.42—1.32(m, 2H, OCH₂CH₂CH₂·CH₂CH₂CH₃), 1.32—1.21(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.85(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₂CH₃)	170.8(C1a), 157.5, 157.3(C1b, C7a), 147.5(C2b), 145.3(C5b), 138.5(C4c), 130.3(2C), 129.6(C4a), 129.3(2C), 128.3(2C), 126.2(C7c), 114.1(C6a, C8a), 113.9, 112.0,(C3b, C4b), 80.3(OCH₂C≡≡CH), 77.4(OCH₂C≡≡CH), 70.4(C1c), 67.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 57.8(OCH₂C≡≡CH), 54.2(C2a), 50.1(C2c), 36.7(C3a), 36.7(C3c), 31.1(OCH₂CH₂CH₂CH₂CH₂CH₃),28.8(OCH₂CH₂CH₂CH₂CH₂CH₃), 25.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 22.2(OCH₂CH₂CH₂·CH₂CH₂CH₃), 14.1(OCH₂CH₂CH₂CH₂·CH₂CH₃)
14a	7.72(d, J=7.7 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.51(t, J=7.2 Hz, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.22—7.05(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.88(d, J=7.5 Hz, 1H, NHCO), 6.82(d, J=8.3 Hz, 2H, 6a-H, 8a-H), 6.40(d, J=8.4 Hz, 1H, NHCO), 6.03(ddd, J=22.0, 10.5, 5.2 Hz, 1H, OCH₂CH CH₂), 5.44—5.34(m, 2H, 4d-H, OCH₂CH CH), 5.29—5.17(m, 2H, 2d-H, OCH₂CH CH), 5.03(dd, J=10.4, 3.2 Hz, 1H, 3d-H), 4.76(dd, J=13.6, 7.2 Hz, 1H, 2a-H), 4.59—4.45(m, 7H, H-1d, OCH₂CH₂—N—N, OCH₂C CH, OCH₂CH CH₂), 4.26—4.07(m, 3H, 2c-H, 6d-H), 3.99—3.83(m, 4H, 5d-H, OCH₂×2), 3.74—3.67(m, 1H, OCH₂), 3.65—3.55(m, 6H, OCH₂×3), 3.40(dd, J=9.2, 3.0 Hz, 1H, 1c-H), 3.25(dd, J=9.2, 3.8 Hz, 1H, 1'c-H), 3.14(dd, J=13.8, 5.7 Hz, 1H, 3a-H), 3.03(dd, J=13.7, 7.8 Hz, 1H, 3'a-H), 2.78(d, J=5.9 Hz, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.98(s, 3H, CH₃CO)	170.6, 170.4, 170.3, 170.2, 170.0(C1a, CH₃CO×4), 167.0(C1b), 157.7(C7a), 144.6(OCH₂C CH), 137.7(C4c), 133.9(C2b), 133.3(OCH₂CH CH₂), 131.9(C5b), 130.5(2C), 129.4(2C), 128.9(C4a), 128.7(C4b, C6b), 128.5(2C), 127.2(C3b, C7b), 126.5(C7c), 123.8(OCH₂C CH), 117.9(OCH₂CH CH₂), 114.9(C6a, C8a), 101.4(C1d), 71.0(C3d), 70.71, 70.69, 70.6, 70.3(C5d, OCH₂×3), 70.0(C1c), 69.6, 69.2(OCH₂×2), 68.9, 68.8(C2d, OCH₂CH CH₂), 67.1(C4d), 64.6(OCH₂·C CH), 61.3(C6d), 55.0(C2a), 50.6(C2c), 50.3(OCH₂CH₂—N—N), 37.8(C3a), 37.4(C3c), 20.9, 20.82, 20.80, 20.7,(CH₃CO×4)
Compd.	¹H NMR(400 MHz), δ^a	¹³C NMR, δ^b
14b	7.77—7.74(m, 2H, 3b-H, 7b-H), 7.65(s, 1H, OCH₂C CH), 7.54—7.49(m, 1H, 5b-H), 7.46—7.41(m, 2H, 4b-H, 6b-H), 7.20—7.06(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.95(d, J=7.7 Hz, 1H, NHCO), 6.81(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.20(d, J=8.6 Hz, 1H, NHCO), 5.39(dd, J=3.4, 1.0 Hz, 1H, 4d-H), 5.20(dd, J=10.5, 7.9 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.76—4.70(m, 1H, 2a-H), 4.58—4.41(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.21—4.05(m, 5H, 6d-H, 2c-H, OCH₂CH₂CH₂OH), 3.98—3.86(m, 4H, 5d-H, OCH₂×2), 3.83(t, J=5.7 Hz, 2H, OCH₂CH₂CH₂OH), 3.70(ddd, J=10.8, 6.2, 4.4 Hz, 1H, OCH₂), 3.63—3.58(m, 6H, OCH₂×3), 3.33(dd, J=9.3, 3.2 Hz, 1H, 1c-H), 3.17(dd, J=13.5, 5.4 Hz, 1H, 1'c-H), 3.09(dd, J=9.3, 3.9 Hz, 1H, 3a-H), 2.95(dd, J=13.5, 8.9 Hz, 1H, 3'a-H), 2.83—2.70(m, 2H, 3c-H), 2.13(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.05—1.99(m, 2H, OCH₂CH₂CH₂OH), 1.98(s, 3H, CH₃CO)	170.6, 170.4, 170.3, 170.1, 169.6(C1a, CH₃CO×4), 166.9(C1b), 158.0(C7a), 144.7(OCH₂C CH), 137.7(C4c), 134.0(C2b), 131.9(C5b), 130.5(2C), 129.4(2C), 128.8(C4a), 128.7(C4b, C6b), 128.5(2C), 127.2(C3b, C7b), 126.6(C7c), 123.7(OCH₂C CH), 114.6(C6a, C8a), 101.4(C1d), 71.0(C3d), 70.7, 70.7, 70.6, 70.3(C5d, OCH₂×3), 69.8(C1c), 69.5, 69.2(OCH₂×2), 68.9(C2d), 67.1(C4d), 65.2(OCH₂CH₂CH₂OH), 64.7(OCH₂C CH), 61.3(C6d), 59.5(OCH₂CH₂CH₂OH), 55.4(C2a), 50.40(C2c, OCH₂CH₂—N—N), 38.3(C3a), 37.4(C3c), 32.2(OCH₂CH₂CH₂OH), 20.9, 20.8, 20.7(CH₃CO×4)
14c	8.27(d, J=8.8 Hz, 2H, 4b-H, 6b-H), 7.90(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.23—7.08(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.80(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.40(d, J=8.4 Hz, 1H, NHCO), 5.39(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.21(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.79—4.72(m, 1H, 2a-H), 4.59—4.50(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.06(m, 3H, 6d-H, 2c-H), 4.01—3.81(m, 6H, 5d-H, OCH₂×3), 3.71(ddd, J=10.7, 6.1, 4.4 Hz, 1H, OCH₂), 3.64—3.56(m, 6H, OCH₂×3), 3.43(dd, J=9.5, 3.6 Hz, 1H, 1c-H), 3.27(dd, J=9.4, 3.9 Hz, 1H, 1'c-H), 3.15(dd, J=13.8, 5.6 Hz, 1H, 3a-H), 3.03(dd, J=13.8, 7.9 Hz, 1H, 3'a-H), 2.86—2.72(m, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.83—1.73(m, 2H, OCH₂CH₂CH₃), 1.01(t, J=7.4 Hz, 3H, OCH₂CH₂CH₃)	170.6, 170.4, 170.3, 169.9, 169.6(C1a, CH₃CO×4), 164.9(C1b), 158.4(C7a), 149.8(C5b), 144.5(OCH₂C CH), 139.7(C4c), 137.7(C2b), 130.5(2C), 129.4(2C), 128.5(2C), 128.4(C3b, C7b), 128.1(C4a), 126.6(C7c), 123.9(C4b, C6b), 123.8(OCH₂·C CH), 114.7(C6a, C8a), 101.5(C1d), 71.0(C3d), 70.8, 70.7, 70.7, 70.3(C5d, OCH₂×3), 69.9(C1c), 69.6, 69.3(OCH₂×3), 68.9(C2d), 67.1(C4d), 64.5(OCH₂·C CH), 61.3(C6d), 55.3(C2a), 50.9(C2c), 50.4(OCH₂CH₂—N—N), 38.0(C3a), 37.4(C3c), 22.7(OCH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃CO×4), 10.7(OCH₂CH₂CH₃)
14d	8.27(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 7.90(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.69(s, 1H, OCH₂C CH), 7.22—7.08(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.42(d, J=8.4 Hz, 1H, NHCO), 5.39(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.21(dd, J=10.5, 7.9 Hz, 1H, 2d-H), 5.04(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.80—4.72(m, 1H, 2a-H), 4.59—4.48(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.24—4.06(m, 3H, 6d-H, 2c-H), 4.03—3.83(m, 6H, 5d-H, OCH₂×3), 3.71(ddd, J=10.7, 6.1, 4.5 Hz, 1H, OCH₂), 3.65—3.54(m, 6H, OCH₂×3), 3.43(dd, J=9.5, 3.6 Hz, 1H, 1c-H), 3.27(dd, J=9.5, 3.9 Hz, 1H, 1'c-H), 3.14(dd, J=13.8, 5.6 Hz, 1H, 3a-H), 3.03(dd, J=13.8, 7.8 Hz, 1H, 3'a-H), 2.87—2.73(m, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.78—1.69(m, 2H, OCH₂CH₂CH₂CH₃), 1.53—1.40(m, 2H, OCH₂CH₂CH₂CH₃), 0.96(t, J=7.4 Hz, 3H, OCH₂CH₂·CH₂CH₃)	170.6, 170.4, 170.3, 169.9, 169.6(C1a, CH₃CO×4), 164.9(C1b), 158.4(C7a), 149.8(C5b), 144.5(OCH₂C CH), 139.7(C4c), 137.7(C2b), 130.5(2C), 129.4(2C), 128.5(2C), 128.4(C3b, C7b), 128.1(C4a), 126.6(C7c), 123.9(C4b, C6b), 123.8(OCH₂·C CH), 114.7(C6a, C8a), 101.5(C1d), 71.0(C3d), 70.8, 70.7, 70.3(C5d, OCH₂×3), 69.9(C1c), 69.6, 69.3(OCH₂×2), 68.9(C2d), 67.8(OCH₂), 67.1(C4d), 64.5(OCH₂C CH), 61.3(C6d), 55.3(C2a), 50.9(C2c), 50.4(OCH₂CH₂—N—N), 38.0(C3a), 37.4(C3c), 31.4(OCH₂CH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃CO×4), 19.4(OCH₂·CH₂CH₂CH₃), 14.0(OCH₂CH₂CH₂CH₃)
14e	7.68(s, 1H, OCH₂C CH), 7.46(d, J=0.9 Hz, 1H, 5b-H), 7.22—7.02(m, 8H, 5a-H, 9a-H, 3b-H, 5c-H—9c-H), 6.94(d, J=8.0 Hz, 1H, NHCO), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.51(dd, J=3.4, 1.7 Hz, 1H, 4b-H), 6.34(d, J=8.6 Hz, 1H, NHCO), 5.39(d, J=3.0 Hz, 1H, 4d-H), 5.21(dd, J=10.4, 8.0 Hz, 1H, 2d-H), 5.03(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.71(dd, J=14.0, 7.7 Hz, 1H, 2a-H), 4.59—4.51(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.08(m, 3H, 6d-H, 2c-H), 4.00—3.84(m, 6H, 5d-H, OCH₂×3), 3.74—3.67(m, 1H, OCH₂), 3.65—3.55(m, 6H, OCH₂×3), 3.37(dd, J=9.4, 3.4 Hz, 1H, 1c-H), 3.22(dd, J=9.4, 4.2 Hz, 1H, 1'c-H), 3.10(dd, J=13.8, 6.0 Hz, 1H, 3a-H), 2.99(dd, J=13.8, 7.8 Hz, 1H, 3'a-H), 2.77(dd, J=7.2, 2.9 Hz, 2H, 3c-H), 2.14(s, 3H, CH₃CO), 2.04(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.99(s, 3H, CH₃CO), 1.79—1.69(m, 2H, OCH₂CH₂CH₂CH₂CH₃), 1.47—1.30(m, 4H, OCH₂CH₂CH₂·CH₂CH₃), 0.91(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	170.4, 170.2, 170.2, 169.8, 169.4(C1a, CH₃CO×4), 158.0, 157.8(C1b, C7a), 147.3(C2b), 144.4, 144.2(C5b, OCH₂C CH), 137.5(C4c), 130.3(2C), 129.3(2C), 128.3(2C), 128.1(C4a), 126.3(C7c), 123.6(OCH₂C CH), 114.6(C3b), 114.5(C6a, C8a), 112.1(C4b), 101.2(C1d), 70.8(C3d), 70.5, 70.1(C5d, OCH₂×3), 69.7(C1c), 69.4, 69.1(OCH₂×2), 68.7(C2d), 67.8(OCH₂), 66.9(C4d), 64.4(OCH₂C CH), 61.2(C6d), 54.2(C2a), 50.3, 50.2(C2c, OCH₂·CH₂—N—N), 37.6(C3a), 37.2(C3c), 28.9(OCH₂CH₂CH₂CH₂CH₃), 28.1(OCH₂·CH₂CH₂CH₂CH₃), 22.4(OCH₂CH₂CH₂·CH₂CH₃), 20.8, 20.7, 20.6(CH₃CO×4), 14.0(OCH₂CH₂CH₂CH₂CH₃)
14f	7.67(s, 1H, OCH₂C CH), 7.45(dd, J=1.7, 0.8 Hz, 1H, 5b-H), 7.19—7.04(m, 8H, 5a-H, 9a-H, 3b-H, 5c-H—9c-H), 6.92(d, J=8.0 Hz, 1H, NHCO), 6.78(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.50(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 6.30(d, J=8.6 Hz, 1H, NHCO), 5.38(dd, J=3.4, 0.9 Hz, 1H, 4d-H), 5.20(dd, J=10.5, 8.0 Hz, 1H, 2d-H), 5.02(dd, J=10.5, 3.4 Hz, 1H, 3d-H), 4.74—4.66(m, 1H, 2a-H), 4.60—4.49(m, 5H, 1d-H, OCH₂CH₂—N—N, OCH₂C CH), 4.25—4.07(m, 3H, 6d-H, 2c-H), 3.99—3.85(m, 6H, 5d-H, OCH₂×3), 3.70(ddd, J=10.8, 6.2, 4.5 Hz, 1H, OCH₂), 3.63—3.55(m, 6H, OCH₂×3), 3.37(dd, J=9.4, 3.5 Hz, 1H, 1c-H), 3.22(dd, J=9.4, 4.2 Hz, 1H, 1'c-H), 3.09(dd, J=13.8, 6.0 Hz, 1H, 3a-H), 2.99(dd, J=13.8, 7.7 Hz, 1H, 3'a-H), 2.76(dd, J=7.2, 2.2 Hz, 2H, 3c-H), 2.13(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 2.03(s, 3H, CH₃CO), 1.98(s, 3H, CH₃CO), 1.77—1.69(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.47—1.37(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.35—1.27(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.88(t, J=7.0 Hz, 3H, OCH₂CH₂CH₂CH₂CH₂CH₃)	170.5, 170.4, 170.3, 170.0, 169.6(C1a, CH₃CO×4), 158.2, 158.0(C1b, C7a), 147.5(C2b), 144.6, 144.4(C5b, OCH₂C CH), 137.7(C4c), 130.4(2C), 129.4(2C), 128.4(2C), 128.3(C4a), 126.5(C7c), 123.8(OCH₂C CH), 114.8(C3b), 114.7(C6a, C8a), 112.2(C4b), 101.4(C1d), 71.0(C3d), 70.7, 70.6, 70.3(C5d, OCH₂×3), 69.9 (C1c), 69.6, 69.2(OCH₂×2), 68.9(C2d), 68.0(OCH₂), 67.1(C4d), 64.5(OCH₂C CH), 61.3(C6d), 54.3(C2a), 50.5, 50.3(C2c, OCH₂CH₂—N—N), 37.7(C3a), 37.3(C3c), 31.7(OCH₂CH₂CH₂CH₂CH₂CH₃), 29.3(OCH₂CH₂CH₂CH₂CH₂CH₃), 25.8(OCH₂·CH₂CH₂CH₂CH₂CH₃), 22.7(OCH₂CH₂·CH₂CH₂CH₂CH₃), 20.9, 20.8, 20.7(CH₃·CO×4), 14.2(OCH₂CH₂CH₂CH₂CH₂CH₃)

Table 4 Appearance, yields, specific rotation and HRMS data for target compounds 15a—15f

Compd.	Appearance	Yield(%)	[α $] D 20$ /(°)(c 0.5, CH₃OH)	HRMS(calcd.), m/z
15a	Pale oil	92	-26.1	856.3751(856.3745) [M+Na]⁺
15b	Pale oil	95	-24.0	874.3842(874.3851) [M+Na]⁺
15c	Pale oil	90	-16.0	903.3759(903.3752) [M+Na]⁺
15d	Pale oil	95	-29.9	917.3917(917.3909) [M+Na]⁺
15e	Pale oil	86	-32.0	854.4193(854.4188) [M+H]⁺
15f	Pale oil	85	-40.0	890.4172(890.4164) [M+Na]⁺

Table 4 Appearance, yields, specific rotation and HRMS data for target compounds 15a—15f

Compd.	Appearance	Yield(%)	[α $] D 20$ /(°)(c 0.5, CH₃OH)	HRMS(calcd.), m/z
15a	Pale oil	92	-26.1	856.3751(856.3745) [M+Na]⁺
15b	Pale oil	95	-24.0	874.3842(874.3851) [M+Na]⁺
15c	Pale oil	90	-16.0	903.3759(903.3752) [M+Na]⁺
15d	Pale oil	95	-29.9	917.3917(917.3909) [M+Na]⁺
15e	Pale oil	86	-32.0	854.4193(854.4188) [M+H]⁺
15f	Pale oil	85	-40.0	890.4172(890.4164) [M+Na]⁺

Table 5 1H NMR and 13C NMR data for target compounds 15a—15f*

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
15a	7.97(s, 1H, OCH₂C CH), 7.70(d, J=7.3 Hz, 2H, 3b-H, 7b-H), 7.51(t, J=7.4 Hz, 1H, 5b-H), 7.42(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.17—7.04(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.00(ddd, J=22.4, 10.5, 5.2 Hz, 1H, OCH₂CH CH₂), 5.33(dd, J=17.3, 1.6 Hz, 1H, OCH₂CH CH), 5.19(dd, J=10.6, 1.4 Hz, 1H, OCH₂·CH CH), 4.74(t, J=7.5 Hz, 1H, 2a-H), 4.62—4.49(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.45(d, J=5.2 Hz, 2H, OCH₂CH CH₂), 4.22(d, J=7.5 Hz, 1H, 1d-H), 4.19—4.14(m, 1H, 2c-H), 3.99—3.92(m, 1H, OCH₂), 3.86(t, J=4.1 Hz, 2H, OCH₂), 3.80(d, J=2.9 Hz, 1H, 4d-H), 3.77—3.63(m, 3H, 6d-H, OCH₂), 3.62—3.26(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.03(dd, J=13.7, 6.8 Hz, 1H, 3a-H), 2.95—2.81(m, 2H, 3'a-H, 3c-H), 2.73(dd, J=13.5, 7.6 Hz, 1H, 3'c-H)	173.1(C1a), 169.8(C1b), 158.9(C7a), 145.6(OCH₂C CH), 139.4(C4c), 135.3(C2b), 135.0(OCH₂CH CH₂), 132.9(C5b), 131.5(C5a, C9a), 130.6(C4a), 130.4(C6c, C8c), 129.6(C4b, C6b), 129.4(C5c, C9c), 128.5(C3b, C7b), 127.3(C7c), 126.0(OCH₂·C CH), 117.5(OCH₂CH CH₂), 115.7(C6a, C8a), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.5, 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.7, 69.6(OCH₂, OCH₂CH CH₂), 64.9(OCH₂·C CH), 62.6(C6d), 56.8(C2a), 52.1(C2c), 51.5(OCH₂CH₂—N—N), 38.3(C3a), 38.2(C3c)
15b	7.98(s, 1H, OCH₂C CH), 7.71(dd, J=5.2, 3.3 Hz, 2H, 3b-H, 7b-H), 7.55—7.48(m, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.17—7.05(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.80(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 4.75(dd, J=8.0, 6.9 Hz, 1H, 2a-H), 4.59—4.50(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.21—4.13(m, 1H, 2c-H), 4.02—3.94(m, 3H, OCH₂, OCH₂CH₂CH₂OH), 3.89—3.85(m, 2H, OCH₂), 3.81(d, J=2.6 Hz, 1H, 4d-H), 3.75—3.67(m, 5H, 6d-H, OCH₂, OCH₂CH₂CH₂OH), 3.63—3.28(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.04(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.95—2.82(m, 2H, 3'a-H, 3c-H), 2.74(dd, J=13.6, 7.6 Hz, 1H, 3'c-H), 1.99—1.88(m, 2H, OCH₂CH₂CH₂OH)	173.1(C1a), 169.8(C1b), 159.4(C7a), 145.6(OCH₂C CH), 139.4(C4c), 135.3(C2b), 132.9(C5b), 131.5(C5a, C9a), 130.4(C6c, C8c), 130.3(C4a), 129.6(C4b, C6b), 129.4(C5c, C9c), 128.5(C3b, C7b), 127.3(C7c), 126.0(OCH₂C CH), 115.4(C6a, C8a), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 65.6(OCH₂CH₂CH₂OH), 64.9(OCH₂C CH), 62.6(C6d), 59.6(OCH₂CH₂CH₂OH), 56.8(C2a), 52.1(C2c), 51.5(OCH₂CH₂—N—N), 38.3(C3a), 38.2(C3c), 33.4(OCH₂CH₂CH₂OH)
15c	8.81(d, J=8.5 Hz, 1H, NHCO), 8.28(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.11(d, J=8.4 Hz, 1H, NHCO), 8.04(s, 1H, OCH₂·C CH), 7.98(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.21—7.09(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.77(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.86(d, J=3.8 Hz, 1H, OH), 4.72(d, J=4.3 Hz, 1H, OH), 4.66—4.58(m, 2H, 2a-H), 4.51—4.46(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.38(d, J=4.4 Hz, 1H, OH), 4.10—4.01(m, 2H, 1d-H, 2c-H), 3.85—3.76(m, 4H, OCH₂×2), 3.63—3.20(m, 16H, 1c-H, 2d-H—6d-H, OCH₂×4), 2.94—2.63(m, 4H, 3a-H, 3c-H), 1.71—1.60(m, 2H, OCH₂CH₂CH₃), 0.91(t, J=7.4 Hz, 3H, OCH₂CH₂CH₃)	170.9(C1a), 164.7(C1b), 157.3(C7a), 149.2(C5b), 143.8(OCH₂C CH), 139.8(C4c), 138.6(C2b), 130.3(2C), 129.9(C4a), 129.3(2C), 129.0(C3b, C7b), 128.3(2C), 126.2(C7c), 124.5(OCH₂C CH), 123.6(C4b, C6b), 114.1(C6a, C8a), 103.7(C1d), 75.3(C5d), 73.6(C3d), 70.7(C1c), 70.6(C2d), 69.8, 69.7(OCH₂×3), 68.9(OCH₂×2), 68.3(C4d), 67.9(OCH₂), 63.7(OCH₂C CH), 60.6(C6d), 55.4(C2a), 50.3(C2c), 49.5(OCH₂CH₂—N—N), 36.7(C3a), 36.6(C3c), 22.2(OCH₂CH₂CH₃), 10.6(OCH₂CH₂CH₃)
15d	8.80(d, J=8.5 Hz, 1H, NHCO), 8.28(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.09(d, J=8.4 Hz, 1H, NHCO), 8.04(s, 1H, OCH₂·C CH), 7.98(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.21—7.10(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.77(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 4.84(d, J=4.3 Hz, 1H, OH), 4.70(d, J=5.1 Hz, 1H, OH), 4.67—4.57(m, 2H, 2a-H), 4.52—4.45(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.37(d, J=4.5 Hz, 1H, OH), 4.11—4.01(m, 2H, 1d-H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₃), 3.79(t, J=5.2 Hz, 2H, OCH₂), 3.64—3.20(m, 16H, 1c-H, 2d-H—6d-H, OCH₂×4), 2.95—2.64(m, 4H, 3a-H, 3c-H), 1.66—1.58(m, 2H, OCH₂CH₂CH₂CH₃), 1.43—1.32(m, 2H, OCH₂CH₂CH₂CH₃), 0.88(t, J=7.4 Hz, 3H, OCH₂CH₂CH₂CH₃)	170.9(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 143.8(OCH₂C CH), 139.8(C4c), 138.6(C2b), 130.3(2C), 129.9(C4a), 129.3(2C), 129.0(C3b, C7b), 128.2(2C), 126.2(C7c), 124.5(OCH₂C CH), 123.6(C4b, C6b), 114.1(C6a, C8a), 103.7(C1d), 75.3(C5d), 73.6(C3d), 70.7(C1c), 70.6(C2d), 69.8, 69.6, 68.8(OCH₂×4), 68.3(C4d), 67.8(OCH₂), 67.0(OCH₂CH₂CH₂CH₃), 63.7(OCH₂C CH), 60.6(C6d), 55.4(C2a), 50.3(C2c), 49.5(OCH₂CH₂—N—N), 36.7(C3a), 36.6(C3c), 30.9(OCH₂CH₂CH₂CH₃), 18.9(OCH₂CH₂CH₂CH₃), 13.8(OCH₂CH₂·CH₂CH₃)
15e	7.99(s, 1H, OCH₂C CH), 7.65(dd, J=1.8, 0.8 Hz, 1H, 5b-H), 7.16—7.05(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.57(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.71(dd, J=7.7, 6.9 Hz, 1H, 2a-H), 4.63—4.47(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.19—4.12(m, 1H, 2c-H), 3.97(ddd, J=10.4, 4.9, 3.5 Hz, 1H, OCH₂), 3.90—3.84(m, 4H, OCH₂CH₂—N—N, OCH₂CH₂CH₂CH₂CH₃), 3.81(dd, J=3.3, 0.9 Hz, 1H, 4d-H), 3.77—3.65(m, 3H, 6d-H, OCH₂), 3.63—3.28(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.01(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.93—2.81(m, 2H, 3'a-H, 3c-H), 2.72(dd, J=13.5, 7.6 Hz, 1H, 3'c-H), 1.75—1.67(m, 2H, OCH₂CH₂CH₂CH₂CH₃), 1.44—1.31(m, 4H, OCH₂CH₂CH₂CH₂CH₃), 0.91(t, J=7.1 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	172.7(C1a), 160.1(C1b), 159.4(C7a), 148.5(C2b), 146.5(C5b), 145.5(OCH₂C CH), 139.4(C4c), 131.4(C5a, C9a), 130.4(C4a), 129.9(C6c, C8c), 129.3(C5c, C9c), 127.3(C7c), 125.9(OCH₂C CH), 115.8(C3b), 115.40(C6a, C8a), 113.05(C4b), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.3(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 68.9(OCH₂CH₂CH₂·CH₂CH₃), 64.9(OCH₂C CH), 62.5(C6d), 55.9(C2a), 52.1(C2c), 51.4(OCH₂·CH₂—N—N), 38.4(C3a), 38.1(C3c), 30.1(OCH₂CH₂CH₂CH₂CH₃), 29.4(OCH₂CH₂CH₂·CH₂CH₃), 23.5(OCH₂CH₂CH₂CH₂CH₃), 14.4(OCH₂CH₂CH₂CH₂CH₃)
15f	7.99(s, 1H, OCH₂C CH), 7.65(dd, J=1.7, 0.7 Hz, 1H, 5b-H), 7.17—7.09(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.57(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.70(t, J=7.3 Hz, 1H, 2a-H), 4.59—4.50(m, 4H, OCH₂CH₂-N-N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.18—4.13(m, 1H, 2c-H), 3.98(ddd, J=10.4, 4.9, 3.5 Hz, 1H, OCH₂), 3.91—3.83(m, 4H, OCH₂CH₂—N—N, OCH₂·CH₂CH₂CH₂CH₂CH₃), 3.82(dd, J=3.3, 0.7 Hz, 1H, 4d-H), 3.76—3.66(m, 3H, 6d-H, OCH₂), 3.64—3.27(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.01(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.93—2.81(m, 2H, 3'a-H, 3c-H), 2.72(dd, J=13.5, 7.6 Hz, 1H, 3'c-H), 1.74—1.66(m, 2H, OCH₂CH₂CH₂·CH₂CH₂CH₃), 1.46—1.37(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.36—1.27(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.89(t, J=7.0 Hz, 3H, OCH₂CH₂ CH₂CH₂CH₂CH₃)	172.7(C1a), 160.1(C1b), 159.4(C7a), 148.5(C2b), 146.5(C5b), 145.5(OCH₂C CH), 139.4(C4c), 131.4(C5a, C9a), 130.4(C6c, C8c), 129.9(C4a), 129.3(C5c, C9c), 127.3(C7c), 126.0(OCH₂C CH), 115.8(C3b), 115.4(C6a, C8a), 113.1(C4b), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 68.9(OCH₂CH₂CH₂·CH₂CH₂CH₃), 64.9(OCH₂C CH), 62.5(C6d), 55.9(C2a), 52.1(C2c), 51.4(OCH₂CH₂—N—N), 38.4(C3a), 38.1(C3c), 32.8(OCH₂CH₂CH₂CH₂CH₂CH₃), 30.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 26.9(OCH₂CH₂CH₂·CH₂CH₂CH₃), 23.7(OCH₂CH₂CH₂CH₂CH₂·CH₃), 14.4(OCH₂CH₂CH₂CH₂CH₂CH₃)

Table 5 1H NMR and 13C NMR data for target compounds 15a—15f*

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(101 MHz), δ
15a	7.97(s, 1H, OCH₂C CH), 7.70(d, J=7.3 Hz, 2H, 3b-H, 7b-H), 7.51(t, J=7.4 Hz, 1H, 5b-H), 7.42(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.17—7.04(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.79(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 6.00(ddd, J=22.4, 10.5, 5.2 Hz, 1H, OCH₂CH CH₂), 5.33(dd, J=17.3, 1.6 Hz, 1H, OCH₂CH CH), 5.19(dd, J=10.6, 1.4 Hz, 1H, OCH₂·CH CH), 4.74(t, J=7.5 Hz, 1H, 2a-H), 4.62—4.49(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.45(d, J=5.2 Hz, 2H, OCH₂CH CH₂), 4.22(d, J=7.5 Hz, 1H, 1d-H), 4.19—4.14(m, 1H, 2c-H), 3.99—3.92(m, 1H, OCH₂), 3.86(t, J=4.1 Hz, 2H, OCH₂), 3.80(d, J=2.9 Hz, 1H, 4d-H), 3.77—3.63(m, 3H, 6d-H, OCH₂), 3.62—3.26(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.03(dd, J=13.7, 6.8 Hz, 1H, 3a-H), 2.95—2.81(m, 2H, 3'a-H, 3c-H), 2.73(dd, J=13.5, 7.6 Hz, 1H, 3'c-H)	173.1(C1a), 169.8(C1b), 158.9(C7a), 145.6(OCH₂C CH), 139.4(C4c), 135.3(C2b), 135.0(OCH₂CH CH₂), 132.9(C5b), 131.5(C5a, C9a), 130.6(C4a), 130.4(C6c, C8c), 129.6(C4b, C6b), 129.4(C5c, C9c), 128.5(C3b, C7b), 127.3(C7c), 126.0(OCH₂·C CH), 117.5(OCH₂CH CH₂), 115.7(C6a, C8a), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.5, 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.7, 69.6(OCH₂, OCH₂CH CH₂), 64.9(OCH₂·C CH), 62.6(C6d), 56.8(C2a), 52.1(C2c), 51.5(OCH₂CH₂—N—N), 38.3(C3a), 38.2(C3c)
15b	7.98(s, 1H, OCH₂C CH), 7.71(dd, J=5.2, 3.3 Hz, 2H, 3b-H, 7b-H), 7.55—7.48(m, 1H, 5b-H), 7.43(t, J=7.5 Hz, 2H, 4b-H, 6b-H), 7.17—7.05(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.80(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 4.75(dd, J=8.0, 6.9 Hz, 1H, 2a-H), 4.59—4.50(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.21—4.13(m, 1H, 2c-H), 4.02—3.94(m, 3H, OCH₂, OCH₂CH₂CH₂OH), 3.89—3.85(m, 2H, OCH₂), 3.81(d, J=2.6 Hz, 1H, 4d-H), 3.75—3.67(m, 5H, 6d-H, OCH₂, OCH₂CH₂CH₂OH), 3.63—3.28(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.04(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.95—2.82(m, 2H, 3'a-H, 3c-H), 2.74(dd, J=13.6, 7.6 Hz, 1H, 3'c-H), 1.99—1.88(m, 2H, OCH₂CH₂CH₂OH)	173.1(C1a), 169.8(C1b), 159.4(C7a), 145.6(OCH₂C CH), 139.4(C4c), 135.3(C2b), 132.9(C5b), 131.5(C5a, C9a), 130.4(C6c, C8c), 130.3(C4a), 129.6(C4b, C6b), 129.4(C5c, C9c), 128.5(C3b, C7b), 127.3(C7c), 126.0(OCH₂C CH), 115.4(C6a, C8a), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 65.6(OCH₂CH₂CH₂OH), 64.9(OCH₂C CH), 62.6(C6d), 59.6(OCH₂CH₂CH₂OH), 56.8(C2a), 52.1(C2c), 51.5(OCH₂CH₂—N—N), 38.3(C3a), 38.2(C3c), 33.4(OCH₂CH₂CH₂OH)
15c	8.81(d, J=8.5 Hz, 1H, NHCO), 8.28(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.11(d, J=8.4 Hz, 1H, NHCO), 8.04(s, 1H, OCH₂·C CH), 7.98(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.21—7.09(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.77(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 4.86(d, J=3.8 Hz, 1H, OH), 4.72(d, J=4.3 Hz, 1H, OH), 4.66—4.58(m, 2H, 2a-H), 4.51—4.46(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.38(d, J=4.4 Hz, 1H, OH), 4.10—4.01(m, 2H, 1d-H, 2c-H), 3.85—3.76(m, 4H, OCH₂×2), 3.63—3.20(m, 16H, 1c-H, 2d-H—6d-H, OCH₂×4), 2.94—2.63(m, 4H, 3a-H, 3c-H), 1.71—1.60(m, 2H, OCH₂CH₂CH₃), 0.91(t, J=7.4 Hz, 3H, OCH₂CH₂CH₃)	170.9(C1a), 164.7(C1b), 157.3(C7a), 149.2(C5b), 143.8(OCH₂C CH), 139.8(C4c), 138.6(C2b), 130.3(2C), 129.9(C4a), 129.3(2C), 129.0(C3b, C7b), 128.3(2C), 126.2(C7c), 124.5(OCH₂C CH), 123.6(C4b, C6b), 114.1(C6a, C8a), 103.7(C1d), 75.3(C5d), 73.6(C3d), 70.7(C1c), 70.6(C2d), 69.8, 69.7(OCH₂×3), 68.9(OCH₂×2), 68.3(C4d), 67.9(OCH₂), 63.7(OCH₂C CH), 60.6(C6d), 55.4(C2a), 50.3(C2c), 49.5(OCH₂CH₂—N—N), 36.7(C3a), 36.6(C3c), 22.2(OCH₂CH₂CH₃), 10.6(OCH₂CH₂CH₃)
15d	8.80(d, J=8.5 Hz, 1H, NHCO), 8.28(d, J=8.9 Hz, 2H, 4b-H, 6b-H), 8.09(d, J=8.4 Hz, 1H, NHCO), 8.04(s, 1H, OCH₂·C CH), 7.98(d, J=8.9 Hz, 2H, 3b-H, 7b-H), 7.21—7.10(m, 7H, 5a-H, 9a-H, 5c-H—9c-H), 6.77(d, J=8.6 Hz, 2H, 6a-H, 8a-H), 4.84(d, J=4.3 Hz, 1H, OH), 4.70(d, J=5.1 Hz, 1H, OH), 4.67—4.57(m, 2H, 2a-H), 4.52—4.45(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.37(d, J=4.5 Hz, 1H, OH), 4.11—4.01(m, 2H, 1d-H, 2c-H), 3.86(t, J=6.5 Hz, 2H, OCH₂CH₂CH₂CH₃), 3.79(t, J=5.2 Hz, 2H, OCH₂), 3.64—3.20(m, 16H, 1c-H, 2d-H—6d-H, OCH₂×4), 2.95—2.64(m, 4H, 3a-H, 3c-H), 1.66—1.58(m, 2H, OCH₂CH₂CH₂CH₃), 1.43—1.32(m, 2H, OCH₂CH₂CH₂CH₃), 0.88(t, J=7.4 Hz, 3H, OCH₂CH₂CH₂CH₃)	170.9(C1a), 164.6(C1b), 157.3(C7a), 149.1(C5b), 143.8(OCH₂C CH), 139.8(C4c), 138.6(C2b), 130.3(2C), 129.9(C4a), 129.3(2C), 129.0(C3b, C7b), 128.2(2C), 126.2(C7c), 124.5(OCH₂C CH), 123.6(C4b, C6b), 114.1(C6a, C8a), 103.7(C1d), 75.3(C5d), 73.6(C3d), 70.7(C1c), 70.6(C2d), 69.8, 69.6, 68.8(OCH₂×4), 68.3(C4d), 67.8(OCH₂), 67.0(OCH₂CH₂CH₂CH₃), 63.7(OCH₂C CH), 60.6(C6d), 55.4(C2a), 50.3(C2c), 49.5(OCH₂CH₂—N—N), 36.7(C3a), 36.6(C3c), 30.9(OCH₂CH₂CH₂CH₃), 18.9(OCH₂CH₂CH₂CH₃), 13.8(OCH₂CH₂·CH₂CH₃)
15e	7.99(s, 1H, OCH₂C CH), 7.65(dd, J=1.8, 0.8 Hz, 1H, 5b-H), 7.16—7.05(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.57(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.71(dd, J=7.7, 6.9 Hz, 1H, 2a-H), 4.63—4.47(m, 4H, OCH₂CH₂—N—N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.19—4.12(m, 1H, 2c-H), 3.97(ddd, J=10.4, 4.9, 3.5 Hz, 1H, OCH₂), 3.90—3.84(m, 4H, OCH₂CH₂—N—N, OCH₂CH₂CH₂CH₂CH₃), 3.81(dd, J=3.3, 0.9 Hz, 1H, 4d-H), 3.77—3.65(m, 3H, 6d-H, OCH₂), 3.63—3.28(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.01(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.93—2.81(m, 2H, 3'a-H, 3c-H), 2.72(dd, J=13.5, 7.6 Hz, 1H, 3'c-H), 1.75—1.67(m, 2H, OCH₂CH₂CH₂CH₂CH₃), 1.44—1.31(m, 4H, OCH₂CH₂CH₂CH₂CH₃), 0.91(t, J=7.1 Hz, 3H, OCH₂CH₂CH₂CH₂CH₃)	172.7(C1a), 160.1(C1b), 159.4(C7a), 148.5(C2b), 146.5(C5b), 145.5(OCH₂C CH), 139.4(C4c), 131.4(C5a, C9a), 130.4(C4a), 129.9(C6c, C8c), 129.3(C5c, C9c), 127.3(C7c), 125.9(OCH₂C CH), 115.8(C3b), 115.40(C6a, C8a), 113.05(C4b), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.3(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 68.9(OCH₂CH₂CH₂·CH₂CH₃), 64.9(OCH₂C CH), 62.5(C6d), 55.9(C2a), 52.1(C2c), 51.4(OCH₂·CH₂—N—N), 38.4(C3a), 38.1(C3c), 30.1(OCH₂CH₂CH₂CH₂CH₃), 29.4(OCH₂CH₂CH₂·CH₂CH₃), 23.5(OCH₂CH₂CH₂CH₂CH₃), 14.4(OCH₂CH₂CH₂CH₂CH₃)
15f	7.99(s, 1H, OCH₂C CH), 7.65(dd, J=1.7, 0.7 Hz, 1H, 5b-H), 7.17—7.09(m, 8H, 3b-H, 5a-H, 9a-H, 5c-H—9c-H), 6.76(d, J=8.7 Hz, 2H, 6a-H, 8a-H), 6.57(dd, J=3.5, 1.8 Hz, 1H, 4b-H), 4.70(t, J=7.3 Hz, 1H, 2a-H), 4.59—4.50(m, 4H, OCH₂CH₂-N-N, OCH₂C CH), 4.23(d, J=7.5 Hz, 1H, 1d-H), 4.18—4.13(m, 1H, 2c-H), 3.98(ddd, J=10.4, 4.9, 3.5 Hz, 1H, OCH₂), 3.91—3.83(m, 4H, OCH₂CH₂—N—N, OCH₂·CH₂CH₂CH₂CH₂CH₃), 3.82(dd, J=3.3, 0.7 Hz, 1H, 4d-H), 3.76—3.66(m, 3H, 6d-H, OCH₂), 3.64—3.27(m, 11H, 2d-H, 3d-H, 5d-H, 1c-H, OCH₂×3), 3.01(dd, J=13.8, 6.8 Hz, 1H, 3a-H), 2.93—2.81(m, 2H, 3'a-H, 3c-H), 2.72(dd, J=13.5, 7.6 Hz, 1H, 3'c-H), 1.74—1.66(m, 2H, OCH₂CH₂CH₂·CH₂CH₂CH₃), 1.46—1.37(m, 2H, OCH₂CH₂CH₂CH₂CH₂CH₃), 1.36—1.27(m, 4H, OCH₂CH₂CH₂CH₂CH₂CH₃), 0.89(t, J=7.0 Hz, 3H, OCH₂CH₂ CH₂CH₂CH₂CH₃)	172.7(C1a), 160.1(C1b), 159.4(C7a), 148.5(C2b), 146.5(C5b), 145.5(OCH₂C CH), 139.4(C4c), 131.4(C5a, C9a), 130.4(C6c, C8c), 129.9(C4a), 129.3(C5c, C9c), 127.3(C7c), 126.0(OCH₂C CH), 115.8(C3b), 115.4(C6a, C8a), 113.1(C4b), 105.1(C1d), 76.7(C5d), 74.9(C3d), 72.5(C2d), 71.7(C1c), 71.4, 71.3, 70.4(OCH₂×4), 70.3(C4d), 69.6(OCH₂), 68.9(OCH₂CH₂CH₂·CH₂CH₂CH₃), 64.9(OCH₂C CH), 62.5(C6d), 55.9(C2a), 52.1(C2c), 51.4(OCH₂CH₂—N—N), 38.4(C3a), 38.1(C3c), 32.8(OCH₂CH₂CH₂CH₂CH₂CH₃), 30.4(OCH₂·CH₂CH₂CH₂CH₂CH₃), 26.9(OCH₂CH₂CH₂·CH₂CH₂CH₃), 23.7(OCH₂CH₂CH₂CH₂CH₂·CH₃), 14.4(OCH₂CH₂CH₂CH₂CH₂CH₃)

Scheme 2 Synthetic route Ⅰ for intermediate 5

Scheme 3 Synthetic route Ⅱ for intermediate 5

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基于点击化学反应的半乳糖糖基化马蹄金素衍生物的合成及抗HBV活性

Synthesis and Anti-HBV Activity Evaluation of the Galactopyranosyl Derivatives of MTS Based on Click Reaction^†

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基于点击化学反应的半乳糖糖基化马蹄金素衍生物的合成及抗HBV活性

Synthesis and Anti-HBV Activity Evaluation of the Galactopyranosyl Derivatives of MTS Based on Click Reaction†

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Synthesis and Anti-HBV Activity Evaluation of the Galactopyranosyl Derivatives of MTS Based on Click Reaction^†