2-1、一般步驟

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第五章、實驗步驟及光譜數據

第一節、分析儀器

1. 核磁共振光譜：以 JEOL EX-400 或 Varian Gemini-2000 型核磁共振光譜儀做為測定儀器。樣品之溶劑為氘化氯仿(CDCl3)及氘化苯 (C6D6)，化學位移以 ppm 為單位，¹H NMR 光譜¹³C NMR 光譜化學位移內標的分裂依溶劑之一般標準定義。¹H NMR 光譜的分裂形式的定義：s，單重峰(singlet)；d，雙重峰(doublet)；t，三重峰(tiplet)；

q，四重峰(quartet)；m，多重峰(multiplet)。偶合常數以 J 表示，單 位為Hz。

2. 紅外光譜：以 BIO-RAD FTS-40 FTIR 型光譜儀做為測定儀器，樣品製成純液(neat)或使用礦物油(Nujol)和固體樣品研磨成膏狀再均勻塗抹於聚乙烯膜(PE Film)上，制成透光性良好的的薄膜；光譜單位為波數(cm^-1)。

3. 低解析質譜：使用 TCQ-700 型質譜儀做為測定儀器，離子化電伏 70ev。FAB 質譜使用 MAT-95S 型質譜儀測定，由國科會臺北貴重儀器中心代為測定，記錄形式為質量/電荷(M/Z)，相對強度記錄於括號中，以最高峰為100。

4. 元素分析：使用 Perkin-Elmer 240C 型元素分析儀做為測定儀器，

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由國科會臺北貴重儀器中心代為測定。

5. 熔點測定：使用 Yamato MP-21 型儀器做為測定儀器。

6. X 光單晶繞射:使用 Enraf nonius CAD-4 或 Nonius FR-590 型儀器做為測定儀器，由國科會臺北貴重儀器中心代為測定。

7. 分析用之薄層色層分析片(TLC)：使用 Silica gel 60F245 Merk 薄片展開後，以紫外燈及顯色液檢視。

8. 管柱色層層析：使用 Silica gel 60F，230-240 mesh ATSM Merk 為填充物，用加壓快速層析 (flash column chromatography)依 Still 的操作方法操作，溶劑比例是以體積比配製。

9. 所有反應物和溶劑均為試藥級，純化方法依 D. D. Perrin; W.L.F.

Armarego 及 D. R. Perrin 所著 Purification of Laboratory Chemicals

的方法處理。乙醚，四氫呋喃以鈉金屬和二苯甲酮加熱迴流成藍紫色後蒸餾使用；二氯甲烷以氫化鈣除水後蒸餾使用。

10.高效能液相層析：使用 JASCO model PU-980 型高壓幫浦及 JASCO model UV-970-975 型紫外/可見光檢測器；在管柱選用上使用 CHIRALPAL-AD-H, AS 管柱並以 JASCO-807-IT intergrator 型積分器積分。

11.微量蒸餾裝置：使用 Buchi GKR-51 型儀器操作。

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12.低溫反應控制裝置：使用 NESLAB CC-100 型低溫控制裝置並以工業級異丙醇做為冷劑。

13.旋光儀：使用 Japan JASCO Co. DIP-1000 型 Digital polarimeter 自動旋光光度計。

第二節、VO(OTf)2催化醣類半縮醛反應的實驗步驟及光譜數據

2-1、一般步驟

雙醇2,3-Dihydroxy-propyl benzoate24,¹ 單醣 26-28

、 30-35

²

、 36

³

、 37

⁴依據文獻報導步驟合成. 五碳四醇 25

、

單醣 29

、 32 由ACROS公

司合成販售。所有的液態醛類化合物在使用前乙硫酸鈣乾燥並在減壓條件下蒸餾，固態醇類則以再結晶方式純化。

2-2 VO(OTf)

2催化醣類半縮醛反應通用實驗步驟

取一經真空乾燥處理的 25 毫升的雙頸瓶，一端接通氣頭通氮

氣，另一端以血清篩塞住，在室溫下將 18.5 mg 的 VO(OTf)2-xH2O ( 0.05 毫莫耳, 5 mol % ) 和醛類 ( 1.1-1.30 毫莫耳 ) 加入雙頸瓶中，

並5 毫升以二氯甲烷或乙氰溶解攪拌五分鐘。將雙醇類或是醣類衍生

物 ( 1.0 毫莫耳 ) 加入雙頸瓶中，並持續攪拌。反應過程以薄層分析法 ( TLC ) 分析反應進行，待起始物在 TLC 片完全消失後，立即以 0.5 毫升的三乙基胺 ( Et3N ) 加入反應瓶終止反應。反應溶劑有機層

(4)

以30 毫升乙酸乙酯萃取並以 10 毫升飽和碳酸氫鈉水溶液清洗兩次，

以硫酸鎂乾燥並過濾後抽乾得初產物。初產物可以乙醇再結晶或以

含有1 % 三乙基胺之乙酸乙酯-正己烷溶劑系統利用矽膠快速色層分離法純化。

2-3 產物光譜數據分析

Data for 2-phenyl-1,3-dioxolane:

⁵ ¹

H NMR (400 MHz, CDCl

3

) δ 7.50-7.37 (m, 5H), 5.82 (s, 1H, PhCH), 4.16-4.03 (m, 4H, H

2

C(4), H

2

C(5));

¹³

C NMR (100 MHz, CDCl

3

) δ 137.9, 129.1, 128.3, 126.4, 103.7, 65.2; TLC R

f

0.62 (EtOAc/hexanes, 1/20).

Data for 2-(4-Methoxy-phenyl)-1,3-dioxolane:

⁶ ¹

H NMR (400 MHz, CDCl

3

) δ 7.41 (d, J = 8.7 , 2H), 6.91 (d, J = 8.7 , 2H), 5.76 (s, 1H, PhCH), 4.13-4.01 (m, 4H, H

2

C(4), H

2

C(5));

¹³

C NMR (100 MHz, CDCl

3

) δ 160.2, 129.9, 127.8, 113.6, 103.6, 65.1, 55.1; TLC R

f

0.60 (EtOAc/hexanes, 1/20).

Data for 2-(4-Bromo-phenyl)-1,3-dioxolane:

⁶ ¹

H NMR (400 MHz, CDCl

3

) δ 7.51 (d, J = 8.4 , 2H), 7.35 (d, J = 8.4 , 2H), 5.77 (s, 1H, PhCH), 4.14-3.99 (m, 4H, H

2

C(4), H

2

C(5));

¹³

C NMR (100 MHz, CDCl

3

) δ 137.0, 131.5, 128.2, 123.2, 103.0, 65.3; TLC R

f

0.52 (EtOAc/hexanes, 1/15).

(2-phenyl-1,3-dioxolan-4-ly)methyl benzoate-24’:

H O O

O

H O O

Br

H O O

(5)

1

H NMR (400 MHz, CDCl

3

) δ 8.03 (dd, J = 8.2, 1.2, 2H), 7.59-7.38 (m, 8H, aromatic Hs), 5.53 (s, 1H, PhCH), 5.29 (septet, J = 5.2, 1H, HC(4)), 4.56-4.52 (m, 2H, H

2

COBz), 3.89-3.84 (m, 2H, H

2

C(5));

¹³

C NMR (100 MHz, CDCl

3

) δ 165.4, 137.3, 133.4, 129.7, 129.4, 129.2, 128.5, 128.4, 126.2, 110.5, 77.2, 68.7, 63.2; MS (70 eV, C

17

H

16

O

4

) 284 (M

⁺

, 6), 162 (33), 105 (100), 77 (41); TLC R

f

0.34 (EtOAc/hexanes, 1/50).

3,9-Diphenyl-2,4,8,10-tetraoxa-spiro[5,5]undecane-25’:

1

H NMR (400 MHz, CDCl

3

) δ 7.50-7.48, 7.41-7.36 (m, 10H, 2 × C

6

H

5

), 5.46 (s, 2H, 2 × PhCH), 4.88 (d, J = 11.6 Hz, 2H), 3.87-3.82 (m, 4H), 3.67 (d, J = 11.6 Hz, 2H);

¹³

C NMR (100 MHz, CDCl

3

) δ 137.9, 129.1, 128.3, 126.0, 102.2, 71.0, 70.6, 32.5; MS (70 eV, C

19

H

20

O

4

) 312 (M

⁺

, 87), 311 (100), 205 (24), 175 (40), 105 (60);

TLC R

f

0.46 (EtOAc/hexanes, 1/ 50).

4-Methylphenyl4,6-O-benzylidine-1-thio-β-D-glucopyranoside -26a

1

H NMR (400 MHz, CDCl

3

) δ 7.49-7.43 (m, 4H), 7.38-7.35 (m, 3H), 7.15 (d, J = 8.0, 2H), 5.53 (s, 1H, PhCH), 4.58 (d, J = 9.6, 1H, HC(1)), 4.37 (dd, J = 10.4, 4.0, 1H, H

eq

C(6)), 3.85 (dd, J = 9.6, 8.0, 1H, HC(4)), 3.77 (dd, J = 10.4, 9.6, 1H, H

ax

C(6)), 3.52-3.48 (m, 2H, HC(2), HC(3)), 3.43 (dt, J = 9.6, 4.4, 1H, HC(5)), 2.70 (bs, 1H, OH), 2.60 (bs, 1H, OH), 2.36 (s, 3H, CH

3

);

¹³

C NMR (100 MHz, CDCl

3

) δ 138.9, 136.9, 133.7, 129.9, 129.3, 128.3, 127.2, 126.3, 101.9, 88.7, 80.3, 74.6, 72.5, 70.6, 68.6, 21.2; MS (70 eV, C

20

H

22

O

5

S) 374 (M

⁺

, 34), 250 (100), 145 (10), 127 (19), 124 (77), 107 (71), 91(43), 79 (25); [α]

²⁵_D

-34.40 (c 1.0, CHCl

3

); TLC R

f

0.21 (EtOAc/hexanes, 1/ 2).

O O

O

OO O

O

HO OH

OO

S

(6)

4-Methylphenyl 4,6-O-((4-methoxyphenyl)methylene)-1-thio-β-D-gluco pyranoside-26b:

⁹

1

H NMR (400 MHz, CDCl

3

) δ 7.43 (d, J = 7.7, 2H), 7.39 (d, J = 8.4, 2H), 7.15 (d, J = 7.7, 2H), 6.88 (d, J = 8.3, 2H), 5.48 (s, 1H, PhCH), 4.56 (d, 1H, J = 9.7, HC(1)), 4.35 (dd, J = 10.5, 3.9, 1H, H

eq

C(6)), 3.83-3.73 (m, 2H, H

ax

C(6), HC(4)), 3.82 (s, 3H, OCH

3

), 3.50-3.42 (m, 3H, HC(2), HC(3), HC(5)), 2.79 (bs, 1H, OH), 2.66 (bd, J = 1.4, 1H, OH), 2.36 (s, ArCH

3

);

¹³

C NMR (100 MHz, CDCl

3

) δ 160.3, 138.9, 133.7, 129.9, 129.4, 127.6, 127.2, 113.7, 101.9, 88.7, 80.2, 74.6, 72.5, 70.6, 68.6, 55.3, 21.2; MS (70 eV, C

21

H

24

O

6

S) 404 (M

⁺

, 8), 309 (23), 281 (32), 267 (13), 165 (14), 137 (100), 123 (69); [α]

²⁵_D

-35.70 (c 1.0, CHCl

3

);

TLC R

f

0.19 (EtOAc/hexanes, 1/ 2).

4-Methylphenyl 4,6-O-((4-acetoxyphenyl)methylene)-1-thio-β-D-gluco- pyranoside -26c:

1

H NMR (400 MHz, CDCl

3

) δ 7.49 (d, J = 8.4, 2H), 7.43 (d, J = 8.0, 2H), 7.15 (d, J = 8.0, 2H), 7.09 (d, J = 8.4, 2H), 5.51 (s, 1H, PhCH), 4.56 (d, J = 9.6, 1H, HC(1)), 4.36 (dd, J = 10.4, 4.4, 1H, H

eq

C(6)), 3.78-3.74 (m, 2H, H

ax

C(6), HC(4)), 3.50-3.47 (m, 2H, HC(2), HC(3)), 3.42 (dt, J = 9.6, 4.4, 1H, HC(5)), 2.83 (d, J = 2.4, 1H, OH), 2.68 (d, J = 2.4, 1H, OH), 2.36 (s, 3H, COCH

3

), 2.28 (s, 3H, ArCH

3

);

¹³

C NMR (100 MHz, CDCl

3

) δ 169.2, 151.2, 138.8, 134.6, 133.6, 129.8, 127.5, 127.3, 121.4, 101.2, 88.6, 80.2, 74.5, 72.5, 70.4, 68.5, 21.1, 21.0; MS (70 eV, C

22

H

24

O

7

S) 432 (M

⁺

, 8), 308 (32), 267 (31), 165 (29), 123 (100), 91 (24), 69 (19); [α]

²⁵_D

-19.80 (c 1.0, CHCl

3

); TLC R

f

0.17 (EtOAc/hexanes, 1/ 2); HRMS calcd for (C

22

H

24

O

7

S) 432.1243, found 432.1247; Anal. Calcd. For C

22

H

24

O

7

S: C, 61.10; H,

O HO

OH OO

H₃CO S

O HO

OH OO

O S O

(7)

5.59. Found: C, 60.73; H, 5.61.

4-Methyl phenyl 4,6-O-ethylidene-1-thio-β-D-glucopyranoside -26d:

⁹

1

H NMR (400 MHz, CDCl

3

) δ 7.40 (d, J = 8.0, 2H), 7.13 (d, J = 8.0, 2H), 4.71 (q, J = 5.0, 1H, HCCH

3

), 4.52 (d, J = 9.6, 1H, HC(1)), 4.19 (dd, J = 10.6, 4.6, 1H, H

eq

C(6)), 3.76 (dd, J = 9.6, 9.2, 1H, HC(4)), 3.55 (dd, J = 10.4, 9.6, 1H, H

ax

C(6)), 3.39-3.31 (m, 2H, HC(2), HC(3)), 3.27 (t, J = 9.2, 1H, HC(5)), 3.06 (bs, 1H, OH), 2.81 (bs, 1H, OH), 2.35 (s, 3H, ArCH

3

), 1.36 (d, J = 5.2, 3H, HCCH

3

);

¹³

C NMR (100 MHz, CDCl

3

) δ 138.8, 133.6, 129.9, 127.2, 99.7, 88.7, 79.5, 74.5, 72.5, 70.5, 68.0,

21.2, 20.3; MS (ESI) 335 (M+Na

⁺

, 9); [α]

²⁵_D

-77.12 (c 1.0, CHCl

3

); TLC R

f

0.30 (EtOAc/hexanes, 1/ 2); Anal. Calcd for C

15

H

20

O

5

S (312.4): C, 57.67; H, 6.45. Found:

C, 57.46; H, 6.11.

p-Methylphenyl 2,3-Di-O-Benzyl-4,6-O-benzylidene-1-thio-β-D

-glucopyranoside -27’:

1

Η ΝΜR (500 MHz, CDCl

3

) δ 7.47-7.25 (m, 17H, aromatic Hs), 7.11 (d, J = 8.0, 2H), 5.58 (s, 1H, PhCH), 4.93, 4.92 (d, J = 11.1, 2H, H

2

CPh), 4.82, 4.78 (d, J = 11.1, 2H, H

2

CPh), 4.69 (d, J = 10.0, HC(1)), 4.38 (dd, J = 10.5, 5.0, 1H, H

eq

C(6)), 3.82 (dd, J = 9.5, 9.0, 1H, HC(3)), 3.81 (dd, J = 10.0, 9.0, 1H, H

ax

C(6)), 3.68 (t, J = 9.5, 1H, HC(4)), 3.48 (dd, J = 10.0, 8.5, 1H, HC(2)), 3.45 (ddd, J = 9.5, 9.0, 5.0, HC(5)), 2.34 (s, 3H, ArCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 138.2, 138.1, 138.0, 137.1, 132.9, 129.7, 129.0, 128.9, 128.3, 128.1, 128.1, 128.0, 127.8, 121.7, 125.9, 101.0, 88.4, 82.9, 81.3, 80.2, 75.7, 75.2, 70.1, 68.6, 21.0; MS (FAB, C

34

H

34

O

5

S) m/z 554 (M+H

⁺

, 20); [α]

²⁵_D

-29.9 (c 1.0, CHCl

3

); TLC R

f

0.25 (EtOAc/hexanes, 1/3);

O

HO OH

OO

S

O

O O

OO

S

(8)

HR-FAB MS calcd for C

34

H

34

O

5

S+H: 555.2192, found 555.2205.

p-Methylphenyl-4,6-O-benzylidine-2-deoxy-2-phthalimido-1-thio-β-D-glucopyran oside-28’:

1

H NMR (CDCl

3

, 400 MHz) δ 7.94 (bd, J = 5.6, 2H), 7.76 (dd, J = 5.6, 2.8, 2H), 7.47 (dd, J = 7.6, 4.0, 2H), 7.38-7.36 (m, 3H), 7.28 (d, J = 8.4, 2H), 7.07 (d, J = 8.0, 2H), 5.63 (d, J = 10.5, 1H, HC(1)), 5.56 (s, 1H, PhCH), 4.62 (dt, J = 9.6, 3.2, 1H, HC(3)), 4.39 (dd, J = 10.4, 4.8, 1H, H

eq

C(6)), 4.31 (t, J = 10.0, 1H, HC(2)), 3.82 (t, J = 10.4, 1H, H

ax

C(6)), 3.69 (td, J = 9.3, 4.8, 1H, HC(5)), 3.47 (t, J = 9.2, 1H, HC(4)), 2.55 (bd, J = 1.6, 1H, OH), 2.31 (s, 3H, CH

3

);

13

C NMR (CDCl

3

, 100 MHz) δ 168.2, 167.5, 138.5, 136.9, 134.2, 133.4, 131.6, 129.7, 129.4, 128.4, 127.8, 126.3, 123.9, 123.4, 102.0, 84.5, 82.0, 70.3, 69.8, 68.6, 55.6, 21.1;

MS (70 eV, C

28

H

25

NO

6

S) 503 (M

⁺

, 97), 502 (91), 430 (67), 399 (100), 387 (28), 386 (35); [α]

²⁵_D

+33.4 (c 0.5, CHCl

3

); TLC R

f

0.23 (EtOAc/hexanes, 1/ 2).

Methyl 4,6-O-benzylidene-α-D-glucopyranoside-29a:

1

H NMR (CDCl

3

, 400 MHz) δ 7.51-7.48 (m, 2H), 7.39-7.36 (m, 3H), 5.54 (s, 1H, HC-acetal), 4.81 (d, J = 4.0, 1H, HC(1)), 4.30 (dd, J = 9.6, 4.0, 1H, H

eq

C(6)), 3.94 (t, J = 9.2, 1H, HC(4)), 3.84-3.75 (m, 1H, C(2)), 3.74 (t, J = 9.5, 1H, H

ax

C(6)), 3.64 (dd, J = 9.0, 4.0, 1H, HC(5)), 3.49 (dt, J = 9.2, 4.0, 1H, HC(5)), 3.47 (s, 3H, OCH

3

), 2.66 (d, J = 2.0, 1H, OH), 2.23 (d, J = 9.6, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 137.1, 129.3, 128.3, 126.3, 102.0, 99.8, 80.9, 72.9, 71.9, 68.9, 62.4, 55.6; MS (70 eV, C

14

H

18

O

6

) 282 (M

⁺

, 5), 123 (100), 91 (24); [α]

²⁵_D

+139.00 (c 2.0, CHCl

3

); TLC R

f

0.15

O HO

N OO

S O

O

O HO

HO OO

OCH₃

(9)

(EtOAc/hexanes, 1/ 2).

Methyl-4,6-O-((4-methoxyphenyl)methylene)-α-D-glucopyranoside-29b:

1

H NMR (CDCl

3

, 400 MHz) δ 7.41 (d, J = 8.8, 2H), 6.88 (d, J = 8.8, 2H), 5.48 (s, 1H, HC-acetal), 4.78 (d, J = 4.0, 1H, HC(1)), 4.27 (dd, J = 9.6, 4.4, 1H, H

eq

C(6)), 3.90 (t, J = 9.2, 1H, HC(4)), 3.80 (s, 3H, ArOCH

3

), 3.78-3.76 (m, 1H, HC(2)), 3.72 (dd, J = 9.6, 9.4, 1H, H

ax

C(6)), 3.61 (dt, J = 9.2, 3.9, 1H, HC(5)), 3.46 (t, J = 9.2,1H, HC(3)), 3.45 (s, 3H, OCH

3

), 2.86 (bs, 1H, OH), 2.38 (d, J = 8.8, 1H, OH);

13

C NMR (CDCl

3

, 100 MHz) δ 160.2, 129.5, 127.6, 113.7, 101.9, 99.8, 80.9, 72.9, 71.8, 68.9, 62.4, 55.5, 55.3; MS (70 eV, C

15

H

20

O

7

) 312 (M

⁺

, 28), 311 (31), 137 (93), 135 (100); [α]

²⁵_D

+105.68 (c 1.0, CHCl

3

); TLC R

f

0.45 (MeOH/CH

2

Cl

2

, 1/ 10).

Methyl -4,6-O-((4-acetoxyphenyl)methylene)-α-D-glucopyranoside-29c:

1

H NMR (CDCl

3

, 400 MHz) δ 7.51 (d, J = 8.6, 2H,), 7.10 (d, J = 8.6, 2H), 5.53 (s, 1H, HC-acetal), 4.81 (d, J = 4.0, HC(1)), 4.29 (dd, J = 9.2, 4.0, 1H, H

eq

C(6)), 3.92 (t, J = 9.2, 1H, HC(4)), 3.78 (dd, J = 9.2, 4.4, 1H, HC(2)), 3.76 (dd, J = 10.0, 9.2, 1H, H

ax

C(6)), 3.63 (dd, J = 9.2, 4.0, 1H, HC(5)), 3.51-3.49 (m, 1H, HC(3)), 3.46 (s, 3H, OCH

3

), 2.29 (s, 3H, OC(O)CH

3

), 1.95 (br, 2H, 2 × OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 169.2, 151.2, 137.7, 127.6, 121.4, 101.2, 99.8, 80.9, 72.8, 71.6, 68.9, 62.3, 55.5, 21.1; MS (70 eV, C

16

H

20

O

8

) 340 (M

⁺

, 11), 298 (30), 297 (17), 281 (12), 165 (44), 123 (100), 122(62), 121 (75); [α]

²⁵_D

+105.36 (c 1.0, CHCl

3

); TLC R

f

0.13 (EtOAc/hexanes, 1/ 2); Anal. Calcd For C

16

H

20

O

8

: C, 56.47; H, 5.92. Found: C, 56.20; H, 6.10.

O HO

HO OO

OCH₃ H₃CO

O HO

HO OO

OCH₃ O

O

(10)

Methyl -4,6-O-((2-naphthyl)methylene)-α-D-glucopyranoside-29d:

1

H NMR (CDCl

3

, 400 MHz) δ 7.97 (s, 1H), 7.87-7.82 (m, 3H), 7.60 (dd, J = 8.5, 1.4, 1H), 7.51-7.48 (m, 2H), 5.70 (s, 1H, HC-acetal), 4.81 (d, J = 3.9, 1H, HC(1)), 4.34 (dd, J = 9.5, 4.1, 1H, H

eq

C(6)), 3.96 (dd, J = 9.2, 8.0, 1H, HC(4)), 3.87-3.78 (m, 2H, H

ax

C(6), HC(2)), 3.67 (dt, J = 9.6, 3.9, 1H, HC(5)), 3.54 (t, J = 9.2, 1H, HC(3)), 3.47 (s, 3H, OC(O)CH

3

), 2.78 (bs, 1H, OH), 2.30 (d, J = 9.1, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 134.4, 133.8, 132.9, 128.4, 128.2, 127.7, 126.5, 126.2, 125.8, 123.7, 102.0, 99.8, 81.0, 72.9, 71.9, 69.0, 62.4, 55.6; MS (70 eV, C

18

H

20

O

6

) 332 (M

⁺

, 31), 157 (34), 156 (100), 155 (82), 141(12), 129 (19), 128 (31), 127 (68), 126 (19), 101 (13), 87 (11), 86 (25), 85 (18), 75 (13), 74 (54), 73 (38), 71 (38), 69 (15), 61 (25), 60 (69), 57 (55), 56 (27), 55 (15); [α]

²⁵_D

+82.8 (c 1.0, CHCl

3

);

TLC R

f

0.35 (MeOH/CH

2

Cl

2

, 1/15).

4-Methylphenyl 4,6-O-benzylidine-1-thio-β-D-galactopyranoside -30a:

⁹

1

H NMR (400 MHz, CDCl

3

) δ 7.58 (dd, J = 7.6, 2.0, 2H), 7.39-7.36 (m, 5H, aromatic Hs), 7.12 (d, J = 8.0, 2H), 5.51 (s, 1H, PhCH), 4.47 (d, J = 9.2, 1H, HC(1)), 4.40 (dd, J = 12.4, 1.6, 1H, H

eq

C(6)), 4.22 (d, J = 2.4, 1H, HC(4)), 4.04 (dd, J = 12.4, 1.6, 1H, H

ax

C(6)), 3.71-3.63 (m, 2H, HC(2), HC(3)), 3.56 (d, J = 1.4, 1H, HC(5)), 2.46 (d, J = 1.6, 1H, OH), 2.42 (d, J = 8.4, 1H, OH), 2.36 (s, 3H, ArCH

3

);

13

C NMR (100 MHz, CDCl

3

) δ 138.5, 137.6, 134.3, 129.7, 129.3, 128.2, 126.7, 126.6, 101.4, 87.1, 75.4, 73.8, 70.0, 69.3, 68.7, 21.2; MS (70 eV, C

20

H

224

O

5

S) 374 (M

⁺

, 98), 251 (36), 124 (31), 107 (100), 91 (43), 79 (38); [α]

²⁵_D

-72.8 (c 1.0, MeOH); TLC R

f

0.31 (EtOAc/hexanes, 1/ 2).

O

HO OH

S OO

O HO

HO OO

OCH₃

(11)

4-Methylphenyl 4,6-O-((4-methoxyphenyl)methylene)-1-thio-β-D-galato- pyranoside-30b:

1

H NMR (400 MHz, CDCl

3

) δ 7.58 (d, J = 8.0, 2H), 7.31 (d, J

= 8.6, 2H), 7.12 (d, J = 8.0, 2H), 6.87 (d, J = 8.6, 2H), 5.45 (s, 1H, PhCH), 4.44 (d, J = 8.8, 1H, HC(1)), 4.35 (d, J = 12.4, 1H, H

eq

C(6)), 4.18-4.16 (m, 1H, HC(4)), 4.00 (d, J = 12.4, 1H, H

ax

C(6)), 3.82 (s, 3H, OCH

3

), 3.69-3.59 (m, 2H, HC(2), HC(3)), 3.52-3.50 (bs, 1H, HC(5)), 2.56 (br, 1H, OH), 2.37 (s, ArCH

3

);

¹³

C NMR (100 MHz, CDCl

3

) δ 160.3, 138.5, 134.3, 130.2, 129.7, 127.9, 126.7, 113.5, 101.2, 87.1, 75.3, 73.8, 70.0, 69.3, 68.8, 55.3, 21.3; MS (70 eV, C

21

H

24

O

6

S) 404 (M

⁺

, 7), 309 (19), 281 (32), 267 (9), 137 (100), 123 (79), 91 (30), 69 (19); [α]

²⁵_D

-9.80 (c 1.0, CHCl

3

); TLC R

f

0.23 (EtOAc/hexanes, 1/ 2); HR-MS calcd for C

21

H

24

O

6

404.1294, found 404.1293.

4-Methylphenyl-4,6-O-((4-acetoxyphenyl)methylene)-1-thio-β-D- galato- pyranoside-30c:

1

H NMR (CDCl

3

, 400 MHz) δ 7.57 (d, J = 8.0, 2H), 7.40 (d, J = 8.4, 2H), 7.10 (d, J = 8.0, 2H), 7.07 (d, J = 8.4, 2H), 5.50 (s, 1H, PhCH), 4.45 (d, J = 9.2, 1H, HC(1)), 4.37 (d, J

= 12.0, 1H, H

eq

C(6)), 4.20 (d, J = 2.8, 1H, HC(4)), 4.02 (d, J

= 12.0, 1H, H

ax

C(6)), 3.72-3.59 (m, 2H, HC(2), HC(3)), 3.55-3.54 (bs, 1H, HC(5)), 2.50 (bs, 1H, OH), 2.46 (d, J = 8.4, 1H, OH), 2.38 (s, 3H, ArCH

3

), 2.31 (s, 3H, OC(O)CH

3

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 169.1, 151.2, 138.3, 135.3, 134.0, 129.6, 127.7, 127.0, 121.2, 100.5, 87.0, 75.4, 73.6, 69.8, 69.2, 68.6, 21.1, 21.0; MS (70 eV, C

22

H

24

O

7

S) 432 (M

⁺

, 8), 308 (35),

O

HO OH

S OO

OCH3

O HO

OH S OO

O O

(12)

267 (33), 165 (24), 123 (100), 91 (24); [α]

²⁵_D

-38.80 (c 1.0, CHCl

3

); TLC R

f

0.18 (EtOAc/hexanes, 1/ 2); HR-MS calcd for C

22

H

24

O

7

S 432.1243, found 432.1231; Anal.

Calcd for C

22

H

24

O

7

S: C, 61.10; H, 5.59. Found: C, 60.89; H, 5.34.

p-Methylphenyl 2,3-Di-O-Benzyl-4,6-O-benzylidene-1-thio-^D

-galactopyranoside -31’ :

¹⁰

1

Η ΝΜR (400MHz, CDCl

3

) δ 7.64 (d, J = 8.0, 2H, ), 7.55-7.30 (m, 15H, aromatic Hs), 7.02 (d, J = 8.0, 2H), 5.50 (s, 1H, PhCH), 4.75-4.73 (m, 4H, 2 × H

2

CPh), 4.60 (d, J = 9.2, 1H, HC(1)), 4.38 (d, J = 12.4, 1H, H

eq

C(6)), 4.16 (d, J = 3.2, 1H, HC(4)), 3.98 (dd, J = 12.4, 1H, H

ax

C(6)), 3.87 (t, J = 9.2, 1H, HC(2)), 3.63 (dd, J = 9.2, 3.2, 1H, HC(3)), 3.39 (bs, 1H, HC(5)), 2.32 (s, 3H, CH

3

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 138.5, 138.1, 137.9, 137.6, 133.4, 129.6, 129.0, 128.6, 128.33, 128.27, 128.11, 128.05, 127.74, 127.73, 127.6, 126.6, 101.2, 86.5, 81.4, 75.34, 75.28, 73.6, 71.7, 69.7, 69.4, 21.1; ESI-MS (C

34

H

34

O

5

S, 554) m/z 577 (M+Na

⁺

, 85).

Methyl-4,6-O-benzylidene-α-D–galatopyranoside -32a:

¹¹

1

H NMR (CDCl

3

, 400 MHz) δ 7.51-7.49 (m, 2H), 7.39-7.36 (m, 3H), 5.56 (s, 1H, PhCH), 4.93 (d, J = 3.2, 1H, HC(1)), 4.29 (dd, J = 12.6, 1.4, 1H, H

eq

C(6)), 4.28 (d, J = 3.6, 1H, HC(4)), 4.09 (dd, J = 12.4, 1.6, 1H, H

ax

C(6)), 3.92-3.87 (m, 2H, HC(2), HC(3)), 3.71 (bs, 1H , HC(5)), 3.47 (s, 3H, OCH

3

), 2.09 (bs, 2H, 2 × OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 137.5, 129.0, 128.2, 126.3, 101.3, 100.2, 75.9, 69.9, 69.8, 69.3, 62.7, 55.7; EI-MS (20 eV, C

14

H

18

O

6

) 282 (M

⁺

,12), 251 (7), 179 (19), 162 (8), 133 (22), 107 (100),105(87), 73 (39); [α]

²⁵_D

-110.20 (c 2.0, CHCl

3

); TLC R

f

0.15 (EtOAc/hexanes,

O HO HO

OCH₃ OO

O

O O

S OO

(13)

1/ 2).

Methyl-4,6-O-((4-methoxyphenyl)methylene)-α-D-galatopyranoside-32b:

¹²

1

H NMR (CDCl

3

, 400 MHz) δ 7.42 (d, J = 8.6, 2H), 6.89 (d, J = 8.6, 2H,), 5.51 (s, 1H, PhCH), 4.93 (d, J = 3.2, 1H, HC(1)), 4.29-4.24 (m, 2H, HC(4), H

eq

C(6)), 4.07 (dd, J = 12.6, 1.7, 1H, H

ax

C(6)), 3.92-3.88 (m, 2H, HC(2), HC(3)), 3.81 (s, 3H, ArOCH

3

) 3.69 (s, 1H, HC(5)), 3.46 (s, 3H, OCH

3

), 2.43 (d, J = 8.8, 1H, OH), 2.18 (d, J = 7.6, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 160.3, 130.1, 127.6, 113.6, 101.2, 100.2, 75.8, 69.9, 69.8, 69.3, 62.7, 55.7, 55.3; EI-MS (70 eV, C

15

H

20

O

7

) 312 (M

⁺

, 24), 137 (63), 136 (62), 135 (100), 121 (25); [α]

²⁵_D

+122.60 (c 1.0, CHCl

3

); TLC R

f

0.45 (MeOH/CH

2

Cl

2

, 1/ 10).

Methyl - 4, 6 -O- ((4-acetoxyphenyl)methylene)-α-D-galatopyranoside-32c:

1

H NMR (CDCl

3

, 400 MHz) δ 7.51 (d, J = 8.6, 2H), 7.10 (d, J = 8.6, 2H), 5.56 (s, 1H, PhCH), 4.93 (d, J = 2.4, 1H, HC(1)), 4.31-4.28 (m, 2H, HC(4), H

eq

C(6)), 4.09 (dd, J = 12.6, 1.5, 1H, H

ax

C(6)), 3.91-3.89 (m, 2H, HC(2), HC(3)), 3.71 (s, 1H, HC(5)), 3.47 (s, 3H, OCH

3

), 2.33 (d, J = 4.6, 1H, OH), 2.29 (s, 3H, OC(O)CH

3

), 2.09 (d, J = 2.5, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 169.3, 151.2, 135.2, 127.5, 121.4, 100.6, 100.2, 75.9, 69.83, 69.75, 69.3, 62.7, 55.7, 21.1; EI-MS (70 eV, C

16

H

20

O

8

) 340 (M

⁺

, 12), 298 (33), 297 (17), 281 (13), 165 (43), 123 (100), 122 (62), 121 (79); [α]

²⁵_D

+90.24 (c 1.0, CHCl

3

); TLC R

f

0.45 (MeOH/CH

2

Cl

2

, 1/ 10); Anal.

calcd for C

16

H

20

O

8

: C, 56.47; H, 5.92. Found: C, 56.22; H, 6.10.

O HO

HOOCH₃ OO

OCH₃

O HO HO

OCH₃ OO

O O

(14)

Methyl - 4, 6 -O- ((2-naphthyl)methylene)-α-D-galatopyranoside -32d:

¹³

1

H NMR (CDCl

3

, 400 MHz) δ 7.97 (s, 1H), 7.87-7.82 (m, 3H), 7.60 (dd, J = 8.6, 1.6, 1H), 7.51-7.48 (m, 2H), 5.70 (s, 1H, NpCH), 4.96 (d, J =3.3, 1H, HC(1)), 4.35-4.30 (m, 2H, HC(4), H

eq

C(6)), 4.12 (dd, J = 12.6, 1.5, 1H, H

ax

C(6)), 3.96-3.90 (m, 2H, HC(2), HC(3)), 3.72 (bs, 1H, HC(5)), 3.47 (s, 3H, OCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 134.8, 133.8, 132.9, 128.4, 128.1, 127.7, 126.5, 126.2, 125.7, 123.8, 101.4, 100.2, 76.0, 70.0, 69.9, 69.4, 62.8, 55.8; EI-MS (70 eV C

18

H

20

O

6

) 332 (M

⁺

, 29), 157 (36), 156 (86), 155 (77), 141 (16), 129 (24), 128 (35), 127 (59), 101 (13), 87 (15), 86 (24), 85 (18), 74 (73), 73 (51), 71 (43), 69 (16), 61 (35), 60 (100), 57 (48); [α]

²⁵_D

+99.36 (c 1.0, CHCl

3

); TLC R

f

0.45 (MeOH/CH

2

Cl

2

, 1/ 10).

Methyl-2,3-Di-O-Benzyl-4,6-O-benzylidene-1-α-

^D

-galactopyranoside -33’:

1

Η ΝΜR (500 ΜΗz, CDCl

3

) δ 7.52 (dd, J = 7.5, 1.5, 2H), 7.42-7.24 (m, 13H, aromatic Hs), 5.48 (s, 1H, PhCH), 4.88 (d, J = 12.0, 1H, H

a

H

b

CPh), 4.83 (d, J = 10.0, 1H, H

a

H

b

CPh), 4.77 (d, J

= 3.5, 1H, HC(1)), 4.76 (dd, J = 10.0, 2H, H

a

H

b

CPh), 4.68 (d, J = 12.0, 1H, H

a

H

b

CPh), 4.22 (dd, J = 12.4, 1.3, 1H, H

eq

C(6)), 4.18 (d, 1H, J = 3.1, HC(4)), 4.08 (dd, J = 10.1, 3.5, 1H, HC(3)), 3.97-4.02 (m, 2H, HC(2), H

ax

C(6)), 3.59 (bs, 1H, HC(5)), 3.30 (s, 3H, OCH

3

);

¹³

C NMR (CDCl

3

, 125 MHz) δ 138.8, 138.6, 137.8, 128.8, 128.3, 128.1, 128.0, 127.7, 127.6, 127.5, 126.3, 101.1, 99.5, 76.0, 75.4, 74.8, 73.8, 72.2, 69.4, 62.5, 55.5; FAB-MS (C

28

H

30

O

6

, 462) m/z 463 (M+H

⁺

, 26); TLC R

f

0.25 (EtOAc/hexanes, 1/2).

O

HO HO

OCH₃ OO

BnO O

BnO OCH₃ OO

(15)

Phenyl-3-O-acetyl-2-azido-4,6-benzylidiene-2-deoxy-1-seleno-D-galactopyranosi- de-34a:

¹⁴

1

Η ΝΜR (400 ΜΗz, CDCl

3

) δ 7.59-7.57 (m, 2H), 7.51-7.49 (m, 2H), 7.40-7.39 (m, 3H), 7.30-7.26 (m, 3H), 6.03 (d, J = 5.2, 1H, HC(1)), 5.60 (s, 1H, PhCH), 4.29 (d, J = 3.6, 1H, HC(4)), 4.18-4.12 (m, 3H, HC(2), HC(5), H

eq

C(6)), 4.07 (dd, J = 12.8, 2.0, 1H, H

ax

C(6)), 3.92 (dd, J = 10.4, 3.6, 1H, HC(3)), 2.41 (bs, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 137.1, 133.7, 129.4, 129.2, 128.9, 128.3, 127.7, 126.2, 101.3, 85.2, 74.9, 70.6, 69.0, 65.0, 61.9; FAB-MS (C

19

H

19

N

3

O

4

Se, 432) m/z 433 (M+H

⁺

, 11); TLC R

f

0.21(EtOAc/hexanes, 1/3).

Phenyl-3-O-acetyl-2-azido-4,6-((4-methoxyphenyl)methylene)-2-deoxy-1-seleno-

D

-galactopyranoside -34b:

1

Η ΝΜR (500 ΜΗz, CDCl

3

) δ 7.58-7.56 (m, 2H), 7.41 (d, J = 8.5, 2H), 7.28-7.26 (m, 3H), 6.90 (d, J = 8.5, 2H), 6.03 (d, J = 5.5, 1H, HC(1)), 5.56 (s, 1H, PhCH), 4.30 (d, J = 3.5, 1H, HC(4)), 4.17-4.11 (m, 3H, HC(2), HC(5), H

eq

C(6)), 4.07 (dd, 1H, J = 12.8, 1.8, H

ax

C(6)), 3.94-3.92 (m, 1H, HC(3)), 3.81 (s, 3H, OCH

3

), 2.58 (bs, 1H, OH);

¹³

C NMR (CDCl

3

, 125 MHz) δ 160.4, 133.8, 129.6, 129.2, 128.5, 127.8, 127.6, 113.7, 101.3, 85.2, 74.9, 70.7, 69.1, 65.0, 62.1, 55.3; FAB-MS (C

20

H

21

N

3

O

5

Se,

463) m/z 464 (M+H

⁺

, 15); [α]

²⁵_D

+164.5 (c 1.0, CHCl

3

) TLC R

f

0.24 (EtOAc/hexanes, 1/3); High Resolution FAB-MS calcd for C

20

H

21

N

3

O

5

Se+H: 464.0718, found:

404.0725.

Phenyl-3-O-acetyl-2-azido-4,6-((4-acetoxyphenyl)methylene)-2-deoxy-α-seleno-D-

O HO

N₃SePh OO

HO O

N₃SePh O

O OMe

(16)

galactopyranoside -34c:

1

Η ΝΜR (500 ΜΗz, CDCl

3

) δ 7.58-7.56 (m, 2H), 7.50 (d, J = 9.0, 2H), 7.31-7.26 (m, 3H), 7.11 (d, J = 8.6, 2H), 6.03 (d, J = 5.0, 1H, HC(1)), 5.59 (s, 1H, PhCH), 4.30 (d, J = 3.0, 1H, HC(4)), 4.17-4.11 (m, 3H, HC(2), HC(5), H

eq

C(6)), 4.07 (dd, 1H, J = 12.8, 1.8 Hz, H

ax

C(6)), 3.94-3.92 (m, 1H, HC(3)), 2.56 (bs, 1Hh, OH), 2.29 (s, 3H, OCH

3

);

¹³

C NMR (CDCl

3

, 125 MHz) δ 169.2, 151.4, 134.8, 133.8, 129.2, 128.5, 127.8, 127.5, 121.5, 100.7, 85.2, 74.9, 70.6, 69.1, 65.09, 62.0, 21.9;

FAB-MS (C

21

H

21

N

3

O

6

Se, 491) m/z 492 (M+H

⁺

, 15); [α]

²⁵_D

+169.9 (c 1.0, CHCl

3

);

TLC R

f

0.24 (EtOAc/hexanes, 1/3); High Resolution FAB-MS calcd for C

21

H

21

N

3

O

6

Se+H: 492.0681, found: 492.0674.

p-Methylphenyl 4,6-O-benzylidene-1-thio-α-^D

-mannopyranoside -35’:

1

Η ΝΜR (400 MHz, CDCl

3

) δ 7.52-7.50 (m, 2H), 7.41-7.36 (m, 5H), 7.14 (d, J = 8.0, 2H), 5.58 (s,1H, PhCH), 5.52 (d, J = 1.2, 1H, HC(1)), 4.35 (dt, J = 10.0, 5.2, 1H, HC(5)), 4.31 (dd, J = 3.6, 1.2, 1H, HC(2)), 4.23 (dd, J = 10.4, 5.2, 1H, H

eq

C(6)), 4.14 (dd, J = 9.6, 3.2, 1H, HC(3)), 4.00 (t, J = 9.6, 1H, HC(4)), 3.83 (t, J = 10.4, 1H, H

ax

C(6)), 2.62-2.82 (bd, 1H, OH), 2.34 (s, 3H, CH

3

), 2.33 (bs, 1H, OH);

¹³

C NMR (CDCl

3

, 100 MHz) δ 138.1, 137.1, 132.4, 130.0, 129.43, 129.35, 128.4, 126.3, 102.3, 88.3, 79.0, 72.2, 69.1, 68.5, 64.1, 21.1; FAB-MS (C

20

H

22

O

5

S, 374) m/z 375 (M+H

⁺

, 27); TLC R

f

0.17 (EtOAc/hexanes, 1/2); High Resolution FAB-MS calcd for C

20

H

22

O

5

S+H: 375.1259, found: 375.1266.

Fmoc-Thr(4,6-O-benzylidene-1-β-GulNAc)-O-t-Bu -36a

¹⁵

1

Η ΝΜR (400 ΜΗz, MeOD) δ 7.71 (d, J = 7.5, 2H, Fmoc-HC(4’), HC(5’)), 7.61 (dd, J = 6.8, 2H, Fmoc-HC(1’), HC(8’)), 7.41-7.39 (m, 2H), 7.32-7.21 (m, 7H,

O HO

N₃SePh OO

O O

O HO

OH OO S

(17)

Fmoc-HC(2’, 3’, 6’, 7’) and aromatic Hs), 6.87 (d, J = 8.8, 1H, NH(Thr)), 5.49 (s, 1H, PhCH), 4.50 (s, 1H), 4.44 (d, J = 8.3, 1H, HC(1)), 4.32-4.25 (m, 3H, Fmoc-CH

2,

ThrHC

β

), 4.18-4.14 (m, 2H, Fmoc-HC(9’)

,

HC(3)), 4.04-4.01 (m, 1H, ThrHC

α

), 3.70-3.55 (m, 3H, H

eq

C(6), HC(5), HC(2)), 3.41-3.30 (m, 2H, H

ax

C(6), HC(4)), 1.90 (s, 3H, COCH

3

), 1.39 (s, 9H, C(CH

3

)

3

), 1.06 (d, J = 6.3, 3H, CH

3

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 171.7, 169.2, 156.8, 144.0, 143.8, 141.3, 137.0, 129.2, 128.3, 127.7, 127.1, 126.3, 125.2, 119.9, 101.8, 97.7, 82.2, 81.6, 73.7, 70.3, 68.5, 66.9, 66.1, 58.9, 58.6, 47.2, 28.0, 23.6, 16.4; FAB-MS

(C

38

H

44

N

2

O

10

, 688) m/z 689 (M+H

⁺

, 28); [α]

²⁵_D

–28.1 (c 1.0, CHCl

3

); TLC R

f

0.23 (EtOAc/hexanes, 1/1); High Resolution FAB MS [M+H]

⁺

calcd for C

38

H

44

N

2

O

10

+H:

689.3066, found: 689.3074.

Methyl-(2-(p-methylphenyl)-8,9-O-benzylidene-3,5-dideoxy-5-trifluoroacetamido -2-thio-

D

-glycero-α -galacto-2-nonulopyranosid)onate-37a

¹⁶

1

Η ΝΜR (50 MHz, CD

3

OD): Ιntegration of the intensities of PhCH at δ 5.78 (s, 1H) and 5.62 (s, 1H) showed 1:1 mixture of exo/endo isomers; δ 7.44 (d, J = 8.0, 2H), 7.38 (dd, J = 5.0, 3.0, 1H), 7.33-7.30 (m, 4H), 7.15 (d, J = 7.5, 4.0, 2H), 5.81 (s, 0.5H, PhCH

exo

), 5.65 (s, 0.5H, PhCH

endo

), 4.27-4.24 (m, 1H, HC(8)), 4.18 (d, J = 8.4. 4.9, 1H, H

a

H

b

C(9)), 4.08 (d, J = 8.7, 6.3, 1H, H

a

H

b

C(9)), 3.97-3.91 (m, 2H, HC(5), HC(6)), 3.63-3.56 (m, 2.5H, HC(4), 0.5 × HC(7)), 3.48 (d, J = 7.2, 0.5H, 0.5 × HC(7)), 3.43 (s, 1.5H, OCH

3

), 3.35 (s, 1.5H, OCH

3

), 2.77 (dd, J = 12.7, 4.8, 1H, H

eq

C(3), 2.35 (s, 3H, SC

6

H

4

CH

3

), 1.78 (dd, J = 12.7, 9.0, 1H, H

a

C(3));

¹³

C NMR (CD

3

OD, 125 MHz) δ (two isomers) 170.6, 170.5, 141.8, 141.7, 140.1, 139.1, 138.2, 138.1, 130.7, 130.6, 130.5, 130.2, 129.39, 129.38, 128.0, 127.7, 127.3, 127.2,

O HO NHAc

O HN

O OBu^t OO

Ph

O O

O S O OMe

HO HN HO

O O

Ph

O CF₃

1 2

4 3 5 7 6 9 8

(18)

105.6, 105.3, 88.88, 88.85, 77.70, 76.93, 71.0, 70.9, 69.5, 69.1, 68.9, 68.7, 53.8, 53.7, 52.8, 52.7, 42.0, 21.6, 21.5; FAB-MS (C

26

H

28

F

3

NO

8

S, 571) m/z 572 (M+H

⁺

, 10);

TLC R

f

0.23 (EtOAc/hexanes, 1/2); High resolution FAB-MS calcd for C

26

H

28

F

3

NO

8

S+H: 572.1557, found: 572.1566.

2-4、化合物 38-40 合成方法及步驟

2,3-Di-O-isopropylidene-4-methyl phenyl 4, 6- O-benzylidine-1-thio-β-D-gluco- pyranoside -38c

氣，另一端以血清篩塞住，將 748 毫克 ( 2 mmol )芐基半縮醛保護硫酐葡萄糖

26a 並以 5 毫升四氫呋喃 ( THF ) 溶解，外架冰鍋，降至

0^oC，在氮氣壓下緩慢加入催化量 23 毫克樟腦磺酸 ( 0.1 mol%, champhor sulfonic acid )。隨後以氣密式微量針筒加入 576 毫克 2-甲氧基丙烯 ( 2-methoxypropene, 766 µL, 8 mmol ) 並在室溫下攪拌 1.5

小時。反應隨即以2 毫升冰的飽和碳酸氫鈉水溶液萃息，並以真空幫

浦將溶劑抽亁移除。所得固體初產物以 30 毫升乙酸乙酯溶解並以 10 毫升飽和碳酸氫鈉水溶液清洗兩次，以硫酸鎂乾燥並過濾後抽乾得白色固體。白色固體以 20 毫升熱乙醚溶解再結晶，可得到 780 毫克白色晶狀產物

38，產率 94 %。

O O O

O

O S

38 O O

O

OH

HO S

26a

(19)

1

H NMR (CDCl

3

, 400 MHz) δ 7.49-7.47 (m, 3H, aromatic Hs), 7.36-7.33 (m, 2H, aromatic Hs), 7.15 (d, J = 7.9, 2H), 5.55 (s, 1H, PhCH), 4.86 (d, J = 9.8, 1H, HC(1)), 4.40 (dd, J = 10.5, 4.8, 1H, H

eq

C(6)), 3.87 (t, J = 10.4, 1H, HC(4)), 3.84-3.80 (m, 2H, H

ax

C(6), HC(2)), 3.54-3.47 (m, 1H, HC(3)), 3.31-3.28 (m, 1H, HC(5)), 2.37 (s, 3H, CH

3

), 1.50, 1.46 (s, 6H, C(CH

3

)

2

);

¹³

C NMR (CDCl

3

, 100 MHz) δ 138.8, 136.7, 134.0, 129.6, 129.1, 128.2, 127.1, 126.3, 111.7 (C(CH

3

)

2

), 101.5 (PhCH), 85.5 (C(1)), 79.9, 78.7, 76.1, 72.0, 68.6 (C(2-6)), 26.6 and 26.4 (C(CH

3

)

2

), 21.2 (SC

6

H

4

CH

3

); ESI-MS (C

23

H

26

O

5

S, 415) m/z 438 (M+Na

⁺

, 37); TLC R

f

0.15 (EtOAc/hexanes, 1/ 8); Anal.

Calcd for C

23

H

26

O

5

S: C, 66.64; H, 6.32. Found: C, 66.38; H, 6.37.

4-O-Benzyl-2-O-isopropyl-

4-methylphenyl 4,6-O-benzylidine-1-thio-β-D-gluco- pyranoside-39:

O O O

O

O S

38

O OH O

O

HO S

39

取一經真空乾燥處理的 50 毫升的雙頸瓶，一端接通氣接頭通氮

氣，另一端以血清篩塞住，將830 毫克 38 ( 2 mmol ) 以 10 毫升二氯 甲烷溶解，外架冰鍋，降至0ôC，在氮氣壓下以氣密式針筒緩慢加入 1.0 M 硼烷-四氫呋喃 7 毫升 ( 1.0 M BH3-THF in THF, 7mL, 7 mmol )。隨後以氣密式針筒緩慢加入 250 毫克 VO(OTf)2 ( 0.6 mmol, 0.15 當量 )。反應由 0ôC 逐漸回到室溫並在室溫下攪拌 16 小時直到以TLC 追蹤 38 完全反應消失。反應隨即降至 0ôC 並以 1 毫升三乙基胺萃息反應並緩慢加入過量甲醇 ( 5 毫升 ) 萃息未反應之硼烷，直至

(20)

沒有氣泡產生為止(氫氣)。反應溶劑以減壓濃縮除去得到油狀物，此

油狀物以5 毫升甲醇再度溶解並加入 500 毫克矽膠，甲醇以減壓濃縮除去共揮發 ( co-evaporation ) 兩次。所得固體初產物以乙酸乙酯/正

己烷的混合溶液進行管柱色層分析，可得到 607 毫克固體雙醇產物

39，產率 72% 及部分水解的產物 26 ( 16% )。

1

H NMR (CDCl

3

, 400 MHz) δ 7.38 (d, J = 8.1, 2H), 7.35-7.28 (m, 5H, aromatic Hs), 7.12 (d, J = 8.0, 2H), 4.89 (d, J = 11.3, 1H, H

a

H

b

CPh), 4.69 (d, J = 11.3, 1H, H

a

H

b

CPh), 4.54 (d, J = 9.7, 1H, HC(1)), 4.05 (septet, J = 6.1, 1H, HC(CH

3

)

2

), 3.85 (dd, J = 11.7, 2.5, 1H, H

a

H

b

C(6)), 3.70-3.65 (m, 2H, H

a

H

b

C(6), HC(3)), 3.48 (t, J = 9.4, 1H, HC(4)), 3.35-3.33 (m, 1H, HC(5)), 3.23 (t, J = 9.2, 1H, HC(2)), 2.60 (d, J = 2.0, 1H, OH), 2.33 (s, 3H, SC

6

H

4

CH

3

), 1.97 (t, J = 6.7, 1H, OH), 1.28 (d, J = 6.2, 3H, CHC(CH

3

)

2

), 1.21 (d, J = 6.1, 3H, CHC(CH

3

)

2

);

¹³

C NMR (CDCl

3

, 125 MHz) δ 138.1, 136.7, 132.0, 130.0, 129.8, 128.5. 128.0, 127.9, 88.2 (C(1)), 79.1 (C(2)), 78.9 (C(5)), 78.20 (C(4)), 77.1 (C(3)), 74.7 (PhCH

2

), 73.8 (OCH(CH

3

)

2

), 62.3 (C(6)), 23.1 and 22.4 (OCH(CH

3

)

2

), 21.1 (CH

3

); ESI-MS (C

23

H

30

O

5

S, 418) m/z 441 (M+Na

⁺

, 100);

[α]

²⁵_D

-38.8 (c 1.0, CHCl

3

); TLC R

f

0.27 (EtOAc/hexanes, 1/ 4); Anal. Calcd for C

23

H

30

O

5

S: C, 66.00; H, 7.22. Found: C, 65.62; H, 7.05.

4-Methylphenyl (6-O-acetyl-4-O-benzyl-3-O-(2-chloro)acetyl-2-O-isopropyl)-

1-thio-β-D-gluco- pyranoside-40:

(21)

O O O

O

HO S

39a

O O O

O

O S

O

40 O

O

i

p

o m

i'

p' o'

m' Cl

取一經真空乾燥處理的 50 毫升的雙頸瓶，一端接通氣接頭通氮

氣，另一端外接加液漏斗，加入18.5 毫克 VO(OTf)2 ( 0.05 mmol, 0.05 當量 ) 並以 5 毫升二氯甲烷溶解，在室溫下以微量針筒加入 112 毫克醋酸酐 ( 104 µL, 1.1 mmol ) 攪拌 20 分鐘。外架冰鍋，降至 0^oC，

並將419 毫克雙醇-39 ( 1 mmol ) 溶解於 5 毫升二氯甲烷，在氮氣壓 下以雙針頭轉移至加液漏斗中並緩慢低入上述溶液中。反應於 0^oC 下持續以 TLC 追蹤，約 30 分鐘後起始雙醇完全消失並且 C(6) 1^o醇乙醯基保護

39a 完全升成。隨即將溶解於 3 毫升二氯甲烷之 257 毫克氯

醋酸酐 (chloroacetic anhydride, 1.5 mmol ) 以氣密式針筒緩慢加入上述反應並回到室溫，將加液漏斗置換成回流管並以冷凝水冷凝。隨後將反應加熱至40^oC 於氮氣下回流 8 小時直至 1^o醇乙醯基保護

39a 完

全消失。反應以冰浴降至 0^oC 並以 2 毫升冰的飽和碳酸氫鈉水溶液萃息，並以 30 毫升乙酸乙酯稀釋並以 10 毫升飽和碳酸氫鈉水溶液清洗兩次，有機層以硫酸鎂乾燥並過濾後抽乾得白色固體初產物。初產物以乙酸乙酯/正己烷的混合溶液進行管柱色層分析，可得到 472 毫克產物

40，白色固體，產率 88%。

(22)

1

H NMR (CDCl

3

, 500 MHz) δ 7.42 (d, J = 8.1, 2H), 7.35 (d, J = 6.9, 2H), 7.32 (t, J = 6.9, 1H), 7.25 (t, J = 6.9, 2H), 7.11 (d, J = 8.0, 2H), 5.20 (t, J = 8.8, 1H, HC(3)), 4.58-4.53 (m, 3H, HC(1), OCH

2

Ph), 4.35 (dd, J = 12.0, 1.7, 1H, H

a

H

b

C(6)), 4.20 (dd, J = 11.9 , 4.9, 1H, H

a

H

b

C(6)), 3.94-3.88 (m, 1H, HC(CH

3

)

2

), 3.93 (d, J = 14.9, 1H, ClH

a

H

b

C), 3.85 (d, J = 14.9, 1H, ClH

a

H

b

C), 3.59-3.53 (m, 2H, HC(5), HC(4)), 3.36 (t, J = 9.4, 1H, HC(2)), 2.34 (s, 3H, C(O)CH

3

), 2.07 (s, 3H, SC

6

H

4

CH

3

), 1.23 (d, J = 6.2, 3H, OCHC(CH

3

)

2

), 1.05 (d, J = 6.1, 3H, OCHC(CH

3

)

2

);

¹³

C NMR (CDCl

3

, 125 MHz) δ 170.5 (C(O)CH

3

), 166.0 (C(O)CH

2

Cl) 138.0 (C

i

), 137.2 (C

p

), 132.5 (C

m

), 129.8 (C

i’

), 129.6 (C

o

), 128.6 (C

o’

), 128.2 (C

p’

), 128.0 (C

m’

), 88.8 (C(1)), 79.0 (C(3)), 76.9 (C(2)), 76.6 (C(4)), 76.1 (C(5)), 74.6 (PhCH

2

), 74.0 (OCH(CH

3

)

2

), 63.0 (C(6)), 40.7 (CH

2

Cl), 23.0 (OCH(CH

3

)

2

), 22.1 (OCH(CH

3

)

2

), 21.1 (C(O)CH

3

), 20.8 (SC

6

H

4

CH

3

); ESI-MS

(C

27

H

33

ClO

7

S, 537) m/z 561 (M+Na

⁺

, 9); [α]

²⁵_D

-29.2 (c 1.0, CHCl

3

); TLC R

f

0.20 (EtOAc/hexanes, 1/ 4); Anal. Calcd for C

27

H

33

ClO

7

S: C, 60.38; H, 6.19. Found: C, 60.75; H, 6.06.

4-Methylphenyl (6-O-acetyl-4-O-benzyl-3-O-2-O-isopropyl)-1-thio-β-D-gluco- pyranoside-39a

O OH O

O

HO S

39

O O O

O

HO S

O

39a i

p

o m

i'

p' o'

m'

1

H NMR (CDCl

3

, 400 MHz) δ 7.43 (d, J = 7.8, 2H), 7.41-7.26 (m, 5H, aromatic Hs),

7.10 (d, J = 8.0, 2H), 4.90 (d, J = 11.2, 1H, OCH

a

H

b

Ph), 4.68 (d, J = 11.2, 1H,

OCH

a

H

b

Ph), 4.48 (d, J = 10.0, 1H, HC(1)), 4.34 (dd, J = 11.8, 2.0, 1H, H

a

H

b

C(6)),

4.21 (dd, J = 11.8, 5.6, 1H, H

a

H

b

C(6)), 4.05 (septet, J = 6.1, 1H, HC(CH

3

)

2

), 3.67 (dt,

(23)

J = 8.4, 2.4, 1H, HC(3)), 3.52-3.42 (m, 1H, HC(5)), 3.36 (dd, J = 11.6, 8.4, 1H, HC(4)), 3.25 (t, J = 9.2, 1H, HC(2)), 2.56 (d, J = 2.4, 1H, OH), 2.33 (s, 3H, OC(O)CH

3

), 2.04 (s, 3H, SC

6

H

4

CH

3

), 1.28 (d, J = 6.0, 3H, OCHC(CH

3

)

2

), 1.20 (d, J

= 6.0, 3H, OCHC(CH

3

)

2

);

¹³

C NMR (CDCl

3

, 125 MHz) δ 170.7 (C(O)CH

3

), 137.9 (C

i

), 137.7 (C

p

), 132.1 (C

m

), 130.3 (C

i’

), 129.6 (C

o

), 128.5, 128.1, 128.0 (C

p’

), 88.3 (C(1)), 78.8 (C(2)), 78.5 (C(3)), 76.9 (C(4)), 76.6 (C(5)), 74.6 (OCH

2

Ph), 73.7 (OCH(CH

3

)

2

), 63.5 (C(6)), 23.2 (OC(O)CH

3

), 22.3 (SC

6

H

4

CH

3

), 21.1 (OCH(CH

3

)

2

),

20.8 (OCH(CH

3

)

2

); ESI-MS (C

25

H

32

O

6

S, 460) m/z 483 (M+Na

⁺

, 100).;[α]

²⁵_D

-32.6 (c 1.0, CHCl

3

); TLC R

f

0.35 (EtOAc/hexanes, 1/4); Anal. Calcd for C

25

H

32

O

6

S: C, 65.19;

H, 7.00. Found: C, 65.25; H, 6.70.

第三節、鉬氧金屬錯合物催化醣類衍生物異位性硫基取代反應反應的實驗步驟及光譜數據

3-1 一般步驟

葡萄糖 ( D-Glucose ), 半乳糖 ( D-Galactose ), 甘露糖 ( D-Mannose ), 木糖 ( D-Xylose ), 阿拉伯糖 ( L-arabinose ), 乳糖 ( D-Lactose ), 麥芽糖 ( D-Maltose ), 2, 3, 5-三乙醯基核醣 45 ( 2, 3, 5, Tri-acetyl-β-D-ribofuranoside ) 、Methyltrioxorhenium (VII) (CH₃ReO₃), Chromyl (VI) chloride (CrO2Cl2), Bismuth(III) oxychloride (Bi(O)Cl), Molybdenum (VI) dioxodichlororide (Mo(O)₂Cl₂), Molybdenum acetylacetonate (Mo(O)2(acac)2), Oxomolybdenum (VI) tetrachloride (Mo(O)Cl₄), Molybdenum (V) chloride (MoCl₅), Hafnium(IV)

(24)

oxychloride, Vanadyl (IV) acetyl acetonate (V(O)(acac)2) 由ACROS或 Aldrich公司合成販售。

苯硫醇 ( thiophenol), 4-甲基苯硫醇 ( 4-Methyl thiophenol ), 4-甲氧基苯硫醇 ( 4-Methoxy thiopenol ), 24-甲氧基苯硫醇 ( 2-Methoxy thiophenol ), 1, 3-丙烷雙硫醇 ( 1, 3-propanedithiol ), 乙硫醇 ( ethanethiol ), 環己硫醇 ( Cyclohexyl mercaptan ), 正丁基硫醇 ( t-Butyl mercaptan ), 芐基硫醇 ( Benzyl mercaptan ) 在使用前以硫

酸鈣乾燥並在減壓條件下蒸餾。 1 1 - 硫醇十一酸 ( 11-Mercaptoundecanoic acid ) 使用前以乙醚在結晶

；

4-甲基苯硫醇 ( 4-Methyl thiophenol ), 2-萘基硫醇 ( 2-Naphthalenthiol ), 4-氯基苯硫醇 ( 4-Chlorothiophenol ) 使用前以苯再結晶。五乙醯基葡萄糖 42 ( Penta-O-acetyl-β-D-Glucose )¹⁷,五乙醯半乳糖 43 ( Penta-O- acetyl-β-D-Galactose )¹⁸, 五乙醯甘露糖 44 ( Penta-O-acetyl-β-D -Mannose )¹⁹, 四乙醯木糖 46 ( Tetra-O-acetyl-β-D-Xylose )²⁰, 四乙醯

阿拉伯糖

47 ( Tetra-O-acetyl-α-L-arabinose )

²¹, 2, 3, 5-三乙醯-2, 3- 去氧雙氫基葡萄糖 48 ( 2, 3, 6-triacetyl-glucal ), 七乙醯乳糖 49 ( Hepta-O- acetyl-β-D-Lactose ), 七乙醯麥芽糖 50 ( Hepta-O- acetyl-β-D-Maltose )^{2 2}

, 2-正丁基雙甲基矽烷氧基乙二硫醇

( 2-(t-Butyl dimethylsilyoxy) ethylmercaptan )²³, 11-硫醇十一酸甲酯

(25)

( 11-Mercapto-undecanoic acid methyl ester )²⁴依照文獻合成步驟純化製備。

3-2

過乙醯化醣類硫醣酐化反應之一般合成步驟

氣，另一端以血清篩塞住，將過 1 毫莫耳乙醯化醣類與 11.8 毫克 MoO₂Cl₂( 0.03 mmol, 3 mol% ) 並以5 毫升除氧二氯甲烷 ( 氬氣蒸餾 ) 溶解，在室溫下以微量針筒加入 1.3 毫耳莫芳香基 ( 1.5-2.0 酯肪族硫醇 ) 硫醇，此時溶液呈現藍紫色，攪拌 10 分鐘後溶液呈現綠色，此時以¹ H NMR 追蹤反應發現產物轉換率約 30-45 %，隨後溶液轉換成深褐色並持續以¹ H NMR 及 TLC 分析追蹤反應，12-20 小時後待反應物完全消失，隨即加入冰浴飽和碳酸氫鈉水溶液 3 毫升萃息反應，有機層用二氯甲烷萃取2 次 ( 10 毫升×2 )，取有機層，以硫酸鎂乾燥並過濾後抽乾，將粗產物以乙酸乙酯/正己烷的混合溶液進行管柱色層分析或以乙醇再結晶，可得到硫醣酐產物72-96%。

3-3 硫醣體 41a-50 光譜數據分析

Phenyl 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranoside -41a

²⁵

:

1

H NMR (CDCl

3

, 400 MHz): δ 7.51-7.50 (m, 2 H), 7.32-7.26 (m, 3 H), 5.22 (t, 1H, J = 9.2 Hz), 5.02 (dd,1H, J = 9.8; 9.7

O OAc AcOAcO

OAc S

(26)

Hz), 4.97 (dd, 1H, J = 10.1, 6.1Hz), 4.70 (d, 1H, J = 10.4 Hz), 4.21 (dd, 1H, J = 6.0, 2.8 Hz), 4.19 (dd, 1H, J = 6.0, 2.8 Hz), 3.72 (m, 1H), 2.09, 2.07, 2.01, 1.98 ( each, s, 3H, 4×COCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz): δ 170.51, 170.12, 169.34, 169.2, 133.10, 131.61, 128.9, 128.4, 85.7, 75.8, 73.9, 69.9, 68.2, 62.1, 20.70, 20.7, 20.6, 20.5; M.W. (C

20

H

24

O

9

S) 440.46 ; ESI MS ( m/z 463, [M+Na]

⁺

); White solid; mp 118-120

^o

C; [α]

²³D

–22.7 deg (c 1.0, CHCl

3

); TLC: R

f

= 0.35 (Ethyl acetate/hexane, 1/ 2).

p-Tolyl 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 41b²⁶

:

1

H NMR (CDCl

3

, 400 MHz): δ 7.39 (d, 2 H, J = 8.1 Hz), 7.12 (d, 2 H, J = 7.9 Hz ), 5.21 (t, 1H, J = 9.4 Hz), 5.03 (t,1H, J = 9.4 Hz), 4.94 (t, 1H, J = 9.6 Hz), 4.63 (d, 1H, J = 10.0 Hz), 4.21-4.18 (m, 2H), 3.70 (ddd, 1H, J = 10.1, 4.7, 2.7 Hz), 2.35 (s, 3H), 2.09, 2.08, 2.01, 1.98 ( each, s, 3H, 4×COCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz): δ 170.6, 170.2, 169.4, 169.2, 138.8, 129.7, 127.6, 85.8, 75.8, 74.0, 69.9, 68.2, 62.1, 21.2, 20.7, 20.7,20.6, 20.6; M.W. (C

21

H

26

O

9

S) 454.49 ; ESI MS ( m/z 477, [M+Na]

⁺

);

White crystalline; mp 114-116

^o

C; [α]

²⁴D

–18.2 deg (c 1.2, CHCl

3

); TLC: R

f

= 0.32 (Ethyl acetate/hexane, 1/ 2).

4-Chloro-phenyl 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 41c

²⁷

:

1

H NMR (CDCl

3

, 400 MHz): δ 7.44 (d, 2 H, J = 6.4 Hz), 7.27 (d, 2 H, J = 6.4 Hz ), 5.21 (t, 1H, J = 9.2 Hz ), 5.01 (t, 1H, J = 9.6 Hz), 4.93 (t, 1H, J = 10 Hz), 4.64 (d, 1H, J = 10.0 Hz), 4.25-4.11 (m, 2H), 3.71 (ddd, 1H, J = 10.0, 4.8, 2.8 Hz), 2.07, 2.06, 2.00, 1.97 ( each, s, 3H, 4×COCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz): δ 170.4, 170.1, 169.3, 169.1, 134.9, 129.4, 85.2, 75.8, 73.8, 69.8, 68.1, 62.0, 20.7, 20.6; M.W.

O OAc AcOAcO

OAc S

O OAc AcOAcO

OAc S

Cl

(27)

(C

20

H

23

ClO

9

S) 474.19 ; ESI MS ( m/z 497, [M+Na]

⁺

); White crystalline; mp 112-113

o

C; [α]

²⁶D

–26.4 deg (c 2.0, CHCl

3

); TLC: R

f

= 0.36 (Ethyl acetate/hexane, 1/ 2).

4-Methoxy-phenyl 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 41d

²⁸

:

1

H NMR (CDCl

3

, 400 MHz): δ 7.49 (d, 2 H, J = 10.8 Hz ), 6.84 (d, 2 H, J = 10.8 Hz), 5.17 (t, 1H, J = 9.2 Hz), 4.97 (t, 1H, J = 10.0 Hz), 4.87 (t, 1H, J = 9.6 Hz), 4.53 (d, 1H, J = 10.0 Hz), 4.19 (dd, 1H, J = 12.0, 4.4 Hz), 4.15 (dd, 1H, J = 12.3, 2.2 Hz), 3.80 (s, 3H, ArOCH

3

)), 3.66 (ddd, 1H, J = 7.2, 4.0, 3.2 Hz), 2.08, 2.05, 1.99, 1.96 ( each, s, 3H, 4×COCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz): δ 170.5, 170.1, 169.3, 169.2, 160.4, 136.5, 120.8, 114.4, 85.6, 75.7, 74.0, 69.9, 68.2, 62.0, 55.3, 20.7, 20.7, 20.5, 20.5; M.W. (C

21

H

26

O

10

S) 470.49 ; ESI MS ( m/z 493, [M+Na]

⁺

); White crystalline; mp 92-93

^o

C; [α]

²⁶D

–24.3 deg (c 2.0, CHCl

3

); TLC: R

f

= 0.31 (Ethyl acetate/hexane, 1/ 2).

2-Naphthyl- 2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 41e

²⁹

:

1

H NMR (CDCl

3

, 400 MHz): δ 7.99 (s, 1H), 7.83-7.77 (m,3H), 7.57-7.46 (m, 3H), 5.26 (t, 1 H, J = 9.7 Hz ), 5.11-5.04 (m, 2H), 4.78 (d, 1H, J = 10.0 Hz), 4.23 (dd, 1H, J = 12.3, 5.1 Hz), 4.18 (dd, 1H, J = 12.3, 2.4 Hz), 3.72 (ddd, 1H, J = 7.4, 4.9, 2.4 Hz), 2.11, 2.02, 2.00, 1.98 ( each, s, 3H, 4×COCH

3

);

¹³

C NMR (CDCl

3

, 100 MHz): δ 170.5, 170.1, 169.3, 169.2, 133.4, 132.9, 132.9, 132.7, 130.2, 128.7, 128.4, 127.7, 126.7, 126.6, 85.8, 75.9, 73.9, 70.0, 68.2, 62.1, 20.7, 20.6, 20.52, 20.50; M.W. (C

24

H

26

O

9

S) 490.52 ; ESI MS ( m/z 513, [M+Na]

⁺

); White crystalline;

mp108-109

^o

C; [α]

²⁴D

–16.2 deg (c 1.0, CHCl

3

); TLC: R

f

= 0.36 (Ethyl acetate/hexane, 1/ 2).

O OAc AcOAcO

OAc S

O

O OAc AcOAcO

OAc S