Lie-Feng Ma, Yi-Li Chen, Wei-Guang Shan, and Zha-Jun Zhan · 2020. 2. 14. · 5 2.4 Guaiane and...
33
1 Natural disesquiterpenoids: an update Supplementary Information Lie-Feng Ma, Yi-Li Chen, Wei-Guang Shan, and Zha-Jun Zhan 2 True-disesquiterpenoids .............................................................................................................................2 2.1 Bisabolane sesquiterpenoid dimers (compounds 16) ......................................................................2 2.2 Germacrane sesquiterpenoid dimers (compounds 716) ..................................................................2 2.3 Xanthane sesquiterpenoid dimers (compounds 1735) ....................................................................3 2.4 Guaiane and pseudoguaiane sesquiterpenoid dimers (compounds 36181) .....................................5 2.5 Eremophilane and nardosinane sesquiterpenoid dimers (compounds 182206) ............................13 2.6 Cadinane sesquiterpenoid dimers (compounds 207222)...............................................................15 2.7 Eudesmane and elemane sesquiterpenoid dimers (compounds 223250) ......................................16 2.8 Lindenane sesquiterpenoid dimers (compounds 251341) .............................................................18 2.9 Cuparane, laurane and cyclolaurane sesquiterpenoid dimers (compounds 342345) ....................23 2.10 Sesquiterpenoid alkaloid dimers (compounds 346347) ..............................................................23 2.11 Miscellaneous sesquiterpenoid dimers (compounds 348366).....................................................24 3 Pseudo-disesquiterpenoids .......................................................................................................................25 3.1 Ester linkage (compounds 367401) ...............................................................................................25 3.2 O-ether linkage (compounds 402416) ...........................................................................................28 3.3 Nitrogen and urea linkage (compounds 417427) ..........................................................................29 3.4 Isocitric acid linkage (compounds 428437) ..................................................................................30 3.5 Others (compounds 438447) .........................................................................................................31 4 Merosesquiterpenoid dimers ...................................................................................................................32 Electronic Supplementary Material (ESI) for Natural Product Reports. This journal is © The Royal Society of Chemistry 2020
Transcript of Lie-Feng Ma, Yi-Li Chen, Wei-Guang Shan, and Zha-Jun Zhan · 2020. 2. 14. · 5 2.4 Guaiane and...
1
Natural disesquiterpenoids: an update
Supplementary Information
Lie-Feng Ma, Yi-Li Chen, Wei-Guang Shan, and Zha-Jun Zhan
2 True-disesquiterpenoids.............................................................................................................................2
2.1 Bisabolane sesquiterpenoid dimers (compounds 16) ......................................................................2
2.2 Germacrane sesquiterpenoid dimers (compounds 716) ..................................................................2
2.3 Xanthane sesquiterpenoid dimers (compounds 1735) ....................................................................3
2.4 Guaiane and pseudoguaiane sesquiterpenoid dimers (compounds 36181).....................................5
2.5 Eremophilane and nardosinane sesquiterpenoid dimers (compounds 182206) ............................13
2.6 Cadinane sesquiterpenoid dimers (compounds 207222)...............................................................15
2.7 Eudesmane and elemane sesquiterpenoid dimers (compounds 223250) ......................................16
2.8 Lindenane sesquiterpenoid dimers (compounds 251341).............................................................18
2.9 Cuparane, laurane and cyclolaurane sesquiterpenoid dimers (compounds 342345) ....................23
2.10 Sesquiterpenoid alkaloid dimers (compounds 346347) ..............................................................23
2.11 Miscellaneous sesquiterpenoid dimers (compounds 348366).....................................................24
3 Pseudo-disesquiterpenoids .......................................................................................................................25
3.1 Ester linkage (compounds 367401)...............................................................................................25
3.2 O-ether linkage (compounds 402416)...........................................................................................28
3.3 Nitrogen and urea linkage (compounds 417427) ..........................................................................29
3.4 Isocitric acid linkage (compounds 428437) ..................................................................................30
3.5 Others (compounds 438447) .........................................................................................................31
4 Merosesquiterpenoid dimers ...................................................................................................................32
Electronic Supplementary Material (ESI) for Natural Product Reports.This journal is © The Royal Society of Chemistry 2020
2
2 True-disesquiterpenoids
2.1 Bisabolane sesquiterpenoid dimers (compounds 16)
CH2OH
OH
HO
OH
OH
1 2
COOH
H
COOH
H
A
O
O
HO
O
O
HO
H
O
OH
H
O
3
4
34 7
O
O
HO
O
O
OH
#5 #6
2.2 Germacrane sesquiterpenoid dimers (compounds 716)
OH
O
HO
O
7
O
H
H
H
H
H
O
8
OH
H
H H
O
H
OO
HOR
9 R = H10 R = H
O
AcO
OMe
O
O H
R1
R2
11 R1 = H R2 = Me12 R1 = H R2 = Me
O
AcO
OMe
13
OH
HHO
O
H
O
O
OMe
14
H
OO
O H O
15
O
O O
O
OMe
O
16
3
2.3 Xanthane sesquiterpenoid dimers (compounds 1735)
O
O
H
O
O
O
O
H
H
17
O
O
H
O
O
O
O
H
18
H
O
O
H
O
O
O
O
H
19
O
O
H
O
O
O
O27
H
HO
O
O
H
O
O
O
O28
H
HOHCl
O
O
O
O
O
AcO
29
H
O
O
O
O
O
H
HR
30 R = H31 R = OAc
O
O
32
O
O
OO
H
H H
H
O
O
H
O
O
O
O
H
H13
26
O
O
H
O
O
O
O20 R = H21 R = OH 2'(3')
22 R = OH
H
R
2'3'
O
O
H
O
O
O
O
R
23 R = OAc24 R = H
H
O
O
H
O
O
O
O
H
H
25
O
4
OO
H
O
O
O
O#34
OO
H
O
O
O
O
O
#35
O
O
H
O
O
O
O33
H
H
H H
5
2.4 Guaiane and pseudoguaiane sesquiterpenoid dimers (compounds 36181)
O
O O
OAc
H
O
O
HOH
H
36
O O
OAc
HO
O
OH
37
HO
O O
OAc
HO
O
OH
38
HO
H H H
39 40
O O
OAc
HO
O
OH
41
HO O
OAc
HO
O
OH
H
H
O
O O
OAc
HO
O
OHH
H H
H H
OO
O
H
OO
OHH
O
O
H
H
OH
42 R1 = H R2 = H43 R1 = H R2 = H
OO
OHH
O
O
H
H
OHR1
R2
HO
OO
OHH
O
O
H
H
OH
HO
45
46
OO
OHH
O
O
H
H
HOH
O
44
OO
H
O O
H
O
O
47
49
H
O
COOH
48
H
O
COOHH
COOHH H
HHOOC
H
H
H
50
H
O
COOH
HOOC
H
H
H
HO
H
H
H H
H HH
COOHO
H
COOH
H
R
51 R = H55 R = OH
COOHO
H H
52
HOOC
COOHH H
53 R = H56 R = OH
HO
OOH
R
COOH
H H
HO
OO
HO
54
H
6
O
O
H
OHO
O
OO
O
O
H
OH
O
O
OO
O
57 58
O O
HHO
59O
O
OO
O
H
OO
H
OH
O
OOO
OH
60
O
O
H
HO
61 R = H63 R = H
O
O
O
OH
HO
H
O
O
H
HO
HR
OO
O
O
OHH
R
62 R = H64 R =H
O
O
O R1
O
R3
O65 R1 =OAc R2 = OAc R3 = H66 R1 = OH R2 = OAc R3 = OH67 R1 = OAc R2 = OH R3 = OH
R2
O
O
OAcO
O
OH
O
HO
68
H H
O
O
O
O
HOOH
AcO H
69
O
O
O
O
ROHO
AcO H
H
70 R = Ac71 R = H
H
HO
O
O
OOAcOH
72
O
O
HHOO
O
73
OH
H
HO
OAc
H
H
O
O
R1
O
R2
O
AcO
O H
74 R1 = OAc R2 = OH75 R1 = H R2 = OH76 R1 = OH R2 = H
O
O
HO
AcO
77
COOHO
O
OH
HO
O
78
H
OO
H
O
O
H
HO
80 R = H81 R = H
O
H
H
HO
O
O
82
R O
OO
H
O
O
H
O
79
7
O
O
OAng
OH
OH
O
OH
#84
H
OO
OHH
O
O
H
H
OH
H
#85
OAc O
HO
O
O
O
OAc
#83
87
O
O
HO
H
HH
OH
O
O
HH
OHOAc
OAng OH
HH
O
O
OH
H
H
O
O
88
OR1 OH
HH
O
O
OH
H
H
O
O R2
H
89 R1 = H R2 = H91 R1 = H R2 = OTig92 R1 = Ang R2 = OH93 R1 = Tig R2 = OTig94 R1 = Tig R2 = H
H
OH OH
HH
O
O
OH
H
H
O
O OTig
H
90
OO
OH
H
9897
O
OO
H
H
OAc
#96a R = H#96 R = H
R
OO
OO
O
O
HOAc
O
O
HO
H
99
O
O
O
H
H
OAc
HO
100
O
OO
H
H
OAc
HO
101
OH
H
HO
O
O
H
H
H
OH
OH
#86
O
HO
O
H
HO
HO
O
H
OAc
O
OAc
#95
O
O
H
HR2
OH
OO
102 R2 = O 7,11
103 R2 = O R1 = H104 R2 = OAc 7,11
R1
HO
OO O OH
O
105
HO
H
O OOH
O
106
O
711
8
HO
H
O OOH
O
O
OH
107
H
O
O
O
108
O
O
H
HO
OO
109
O O
H
H
OAc
O
110 111
O
OO
H
H
OAc
O
O
OOH
112
O
O
O
O
113O
H
O
O
O
HO
H
114
O
O HH O
O
115
OO
OH
OH
O
OAc
116
O
O
HO
H O
O
O
O
O
HO
H O
O
OAc
117 118
H H
O
O
HO
H O
O
119
O
O
OH
121
O
O
OHOAc
120
H
H
O
O
O
H
O
122
H
123 124
O
O
O
H
H O
O
O
H
O
H
HO
9
125
O
O
O
H
H O
O
O
H
H
AcO
126
O
O
O
H
H
AcO
127
O O
HOAc
H
128O
O
O
129
H H
H
O
O
HO
130
OH
OAc
H
H HOO
HO
O
O
OH
O
131
O
H O
H
O
132
O
H O
H
O
133
OOTig
H
O
O
O O
HO
OTig
HO
O
134
OO
O
O
O
OH
H
135 136
H
O
OO
O
O
O
OH
H
H
OHOH
H
H
H
O
O
O
O
O
HO
H
H
O
137
HO
O
O
O
O
HO
H
H
OH
138 R = OMe139 R = OEt140 R = H
O
O
OH
H
O
O
O
RO O
141 R = Me142 R = H
R
BzOO
O
R
O
OBz
O
R
143 R = OAc144 R = H
O
O
HO
HOO
H
O
HOH
H
O145
O
H
H
O
HH
O
H
H
O
O
146
10
OO
H
H
H
H
OH
H
O
O
147
O
O
HH
O
H
H
O
O
H
148
O
H
H
O
HH
O
O
O
H
149
O
O
H H
O
H
H
O
O O
H
H
O
HH
O
O
O
150 151
O
O
HH
O
H
H
O
O
H
152
O
H
H
O
HH
O
O
O
H
153
O
H
H
O
HH
O
H
H
O
HO
154
H
O
H
H
O
O O
O
H
H
H
155
H
O
H
H
O
O
O
H
O
H
156
OO
HO
HO
HO
O157 R = H158 R = H
OO
HO
HO
HO O
159
R HH
OO
HO
OH
H
O
O
H
H
OH
HO
OHH
H
OO
161 10,14
163 9.10
O
H
H
O
OH
H
H
O O
H
162
10 914
160
OH
H
O
OHH
HO
OH
H
164
H
OO
H
O
OO
H
165 R = Me167 R = Me
H
OO
H
OO
O
H
166
R
11
H
O
H
O
OO
H
169
O
H
OO
O
H
170
HOH
HOH
H
H
H
OO
H
O
OO
H
168
H
HO
171
O
H
O
HOH
OO
H H
175
H
OO
H
O
OO
H
H
H
H
172
OH
O
H
OO
O
H
O
O
H
H
173
H
OH
O
O
H
H
OO
H
H
H
HO
H
174
H OO
H
O
O
H
HO
176
OO
OO
H
177
OO
O
O
O
O H
H
H
H
H
OO
O
O
O
O H
H
H
H
H
OH
#180a
#179 R = OH#180 R = OH#181 R = H
O
H
O
H
OO
H H
HO
O
OO
H
OHOH
O
HO
HO
#178
R
12
2.5 Eremophilane and nardosinane sesquiterpenoid dimers (compounds 182206)
8
8'O
O
O
O
182 8(R), 8'(S)183 8(S), 8'(R)
O
O
O
O
O
184
OO
OAng
OAng
O
O
OH
OH
185
O O
OH
186
O
OO
OHH
187
OO
OO
H
188
HO
O
O
O
H H
OH
O
O
O
H
HO
189
OOH
R
OHO
190 R =OH191 R = OH192 R = H
O
O
OHO
193
O
O
O
O
194
OAng
AngO
O
O
O
O
OAng
AngO
HH
195 8(S), 8'(R)196 8(R), 8'(S)
8
8'
OO
OH O O OH
O
H
HOH
H
197
O
OH
H
198
OO
HOO
O
O
O
OH H
199
HH
13
N
O
O
O
O
O
OO
200 201
O
O
O
202
O
O
OOH
203
O
O
O
O
204
O
O
OO
OH
205
O
O
O
206
O
14
2.6 Cadinane sesquiterpenoid dimers (compounds 207222)
OHCHO
HO
HO
OH CHO
OH
OH
#207
OHCHO
HO
HO
O
O
CHO
OH
OH
208
O
O
O
HO
OHO
O
O
HO
OHO
209 210
O
O
OOO
211
O
OH
HO
212
O
O
OO O
HOO
OO O
HO
213 214
OOH
HO
OH
O
H
OOH
HO
OH
O
H
215 216
OH
OH
O
OH O
H
217
O
O
HO2C
H
H
H
H
H
O
O
218
O
O
HOH
O
HOH
H OMe
O
O
AcO
219 220
OO
O O
OO
OH
H H
OO
OMeH
H
221 222
H
H
H
H
15
2.7 Eudesmane and elemane sesquiterpenoid dimers (compounds 223250)
OO
O OAcO
#223
H
OH O
HOR
OO
AcO
O
224 R = Ac 225 R = COPri
226 R = MeBu 227 R = Vali
228 R = MeVal
O
H
OO
AcO
O
OH
HO
229
O
H
OO
AcO
O
OH
230
OAc
O
H
OO
AcO
O
OH
231
OOH
OAc O
HOR
OO
AcO
O
232 R = COPri
233 R = MeVal
R
OAc
O
OH
AcO OO
H
234 R = OH235 R = H
OAcCO2H
OO
AcO
236
O
H
OO
R2
O
237 R1 = Ac R2 = OAc238 R1 = H R2 = OAc239 R1 = Ac R2 = H
OR1
OH
H
HO O
H
OO
AcO
O
240
OAc
H
H
OO
O
OAc
H
OO
O
OAc
243
OO
H
OO
HO
241
O
OO
O
H
H#242
16
H
O
OOH
H
O
244
OH
O
H
OO
H
245
O
H
OHR
OOH
H
246 R =H247 R = H
H
O
HO
O
H
HO
248
O
O
O
O
HO
O
O
H
H
O
O
O
O
OH
H
HO
COOMeOH
249
O
H
HO
H
O
O
H
250
17
2.8 Lindenane sesquiterpenoid dimers (compounds 251341)
OH
O
OMeOOC
COOMe
R1 R2
251 R1 = H R2 = H252 R1 + R2 = O253 R1 = H R2 = OH
O
O
MeOOC
H
O
O
HOO
H
H
254
256 R = H257 R = OH
O
OO
OH
OH
H
O
OO
OO
O
O
RHO
H
O
OMeOOCO
HOH
H
OH
H
R1O
OR2
255 R1 = Mesuc R2 = Ang258 R1 = Mesuc R2 = (Z)-Hysen
259
O
OO
OH
OH
H
O
OO
OO
O
O
MeO
OH
O
OMeOOCO
HOH
OH
H
HO
OTig
OOH
O
OMeOOCO
HOH
H
OH
H
O
OO
O
261 R1 = Me R2 = H264 R1 = H R2 = Me
O
R1
O
HOOO
OMeOOCO
HOH
H
OH
H
HO
OTig
262
HOO O
OMeOOCO
HOH
OH
H
O
OO
O
263
O
O
OH
R2
260
O
OMeOOCHO
OHH
H
266
Me
O
OO
HOHH
H
267
COOMe
O
OMeOOCO
HOH
H
OH
H
SucO
OTig
265
18
O
OMeOOCO
HOH
H
OH
H
HO
OAc
274
O
OMeOOCO
R1HH
H
268 R1 = OH R2 = H R3 = OAc269 R1 = OH R2 = OH R3 = H270 R1 = R2 = R3 = H
R2
R3O
O
HOHH
O
O
RO
OH
271 R = H272 R = Bu
O
OMeOOCO
HOH
H
H
HO
OAc
OH
273
O
OMeOOCO
HOH
OH
275
OAc
H
OH
O
OMeOOCO
HOH
H
OH
H
O
OO
O
276
OH
O
O
HOH
R2
H OR3
277 R1 = OH R2 = OH R3 = H278 R1 = OMe R2 = OH R3 = Tig280 R1 = OH R2 = H R3 = Ac
O
OHO
R1
OH
O
O
O
O
OH
OH
H OTig
279
O
OHO
HO
OH
281
O
OO
HOH
OH
H
O
OO
OO
O
O
MeO
O
OO
H
OH
H
O
OO
OO
O
O
O
MeOOC
282
O
O
HO
HH
OH OR
O
O
OOH
283 R = (E)-Hysen
HO OH
O
O
HH
OH OR
284 R = (E)-Hysen
O
O
HOHO
HO
OH
O
O
HOH
OH
H
HO
OO
MeOOC O
OOMeOOC
H
287
O
OMeOOCO
HOHH
285
H
HO
OH
OH
O
OMeOOCO
HOH
H
OH
H
R1O
OR2
286 R1 = Mesuc R2 = Oxsen288 R1 = H R2 = Sen
19
O
O
HOH
OH
H
HO
OO
MeOOC O
OOMeOOC
289
OOH
O
OO
HOH
H
OH
H
O
OO
O
292
O
O
MeO
O
O
O
HOH
OH
H OR2
293 R1 = Mesuc R2 = (E)-Hysen
O
OR1O
HO O
O
HOH
OH
H OR2
294 R1 = Mesuc R2 = (E)-Hysen
O
OR1O
HO
OOH
O
O
HOH
OH
H OR
295 R= (E)-Hysen
O
OHO
HO H
H
296 R= H297 R = OMesuc
O
O
H
OH
O
OHO
COOMe
O
R
H
MeOOC
O
HO
COOMeO
OH
H
300
OHO
MeOOC
H
HO H
H
MeOOC
O
OH
OHO
MeOOC H
H
O
OH
MeOOCH
301302
HO
O
OMeOOC
O
HOH
OH
H
303
OTig O
OO
HOH
H
OH
H
O
OO
OO
O
COOMe
305
O
OMeOOCO
HOH
OH
H
R1O
OR2
OOH
290 R1 = Mesuc R2 = (E)-Hysen291 R1 = R2 = H
298
O
OO
OH
OH
H
O
OO
OO
O
O
EtO
OH
299
O
OO
HOH
OH
H
O
OO
OO
O
O
HO
O
OMeOOCO
HOH
OOH
304
OAc
H
20
O
OMeOOCO
HOH
H
OH
H
R1O
OR2
307 R1 = Suc R2 = (E)-Hysen308 R1 = Mesuc R2 = (E)-Hysen
O
OMeOOCO
HOHH
H
306
AcO
O
OMeOOCO
HOHH
309
Me
H OAc
OO
OO
H
H
310
HO
HO
O
OMeOOCO
HOH
H
H
HO
OR
311 R = Ac315 R = Tig
OH
O
OO
HOHH
O
MeO
R
312 R = OH313 R = OOH
O
OMeOOCO
HOHH
314
OOH
317
O
O
H
OH
OTig
OHO COOMe
OH
HO H
O
O
OH
H
H OAc
316
O
OHO
HO
OH
O
O
H
OH
OTig
OHO COOMe
OH
H
318
O
OMeOOCO
HOH
H
OH
H
O
OO
O
319
O
O
HOO
HO
O
OMeOOCO
HOH
OH
H
O
OO
O
320 R1 = OOH R2 = H321 R1 = OH R2 = Ac
O
OR2O
R1
O
OO
OH
OH
H
O
OO
OO
O
O
HO
OH
AcO
322
O
OMeOOCO
HOH
H
H
HO
OH
323
H
O
OMeOOCO
HOH
O
H
O
OHO
O
324
O
OHO
H
21
O
OMeOOCO
HOH
OH
H
HO
OH
332
H
O
OMeOOCO
HOH
OH
H
O
OO
O
325 R1 = H R2 = OH326 R1 = OH R2 = H328 R1 = OH R2 = OH
O
O
H
R1
R2
O
OMeOOCO
HOH
OH
H OO
331
H
OO
C2H5OOC
OH
O
OMeOOCO
HOH
OH
H
H
O
O
R1O2C R2
OHytig
333 R1 = Me R2 = OH334 R1 = Et R2 = OH
O
OMeOOCO
HOH
OH
H
O
OO
OO
O
H
R1
R2
OH
327 R1 = H R2 = OH329 R1 = OH R2 = OH330 R1 = H R2 = H
O
OMeOOC
O
HO HH
OAc
H
O
O
MeOOCO
HO
H
H
OH
H
O
O
O
O
O
O
R
#335 R = OH#339 R = H
OO
H
OO
H
H
H
#337
O
OMeOOC
O
HOHH
H
#336 #338
#340 R = Tig#341 R = Hysen
O
OMeOOC
O
HOHH
OROH
H
HO
H
22
2.9 Cuparane, laurane and cyclolaurane sesquiterpenoid dimers (compounds 342345)
R
OHO
Br
OHHO
342 R = Br343 R = H
344
OHHOHO OH
#345
2.10 Sesquiterpenoid alkaloid dimers (compounds 346347)
#346
N
S N
H
O
O
H
CH3
OH CH3
OH
#347
NN
CH3H
O
O
S
H
23
2.11 Miscellaneous sesquiterpenoid dimers (compounds 348366)
O
O
O
O
HO
348
O
O
H
OH
HO H
O
O
H
OH
HO H
H
349 350
H
O
O
H
OH
HO
HO351
HO OH
HO OH
O O
H
352 R1 = Me R2 = H353 R1 = Me R2 = H
R1
R2
354 R1 = Me R2 = H355 R1 = Me R2 = H
356 R1 = Me R2 = H357 R1 = Me R2 = H
O
HO2C
H
H
O
R2
HR1H
H
O
HO2C
H
H
O
R2
HR1
O
H O
O
H
O
O
HH
358 R1 = OH R2 = H359 R1 + R2 = O
R1 R2
R1
R2
O
H
O
O
H
OO
H
H
O
R
360 R = H361 R = H
O
H
OH
O
H
OO
H
H
362
OH
OAc
H
H
OH
OH
OR
OHC
OHH
#365 R = Ac#366 R = H
O
O OMeO
OMeO#363 R = -#364R =
H
R
OH
H
H
OH
OH
OR
OHC
OHH
#365a R = Ac#366a R = H
24
3 Pseudo-disesquiterpenoids
3.1 Ester linkage (compounds 367401)
O
H
O
OHO
HO
OHO
367
OO
OHO
HO
OHO
368
O
OH
O
O
O
O
O
HO
O
OO
O
369 5(6) = Z372 5(6) = E
O
O
OH
O
371
O
OO
O
HO
HOOC
HH
O
O
O
HO
HOOC
HH
O
O
OOH
HOOC
OH
H
O
O
OO
373
374 375
OO
O
HOOC
OH
376
56
O
HH
O
HO
O
O
O
O
HO
O
O
O OHOO
O
377
O
HO
O
O
HO
O
O
O OHOO
O
378
OH COOMe
O
O
O
O
OO
O
370
O
OH
O
HO
O
HO
O
O
O OH
379 R =CH2OH380 R = CH2OH
OH COOMe
OR
O O
HO
O
OH
O
OH
O OH
H
O
O
O
O
HO
381
25
O
HO
O
OHO OMe
O
O
HO
O
OHO
HO
O
OO
HO
O
OHO OMe
O
O
HO
O
OHO
HO
O
O
382 383
O
HO
O O
O
O
HO
O
OHO
HO
O
OO
384
H
H
H
O
OH
H
O
H
O
387
O
O
O
O
O
O O
O
O
O
O
O
386
O
OO
OH
H
H
H
O
385
OO
H
O O
OEt
O
H
OO
OH
388
O
H
HOOH
O
O
O
O
H
HO
O
Cl O
O
O
H
H
O
O
COOH
H H
HO
HO
390
OH
O
389 O
O
H
OH
O
O COOH
COOH
OH
OH
O
O
H
OH
O
O
OHO
OH
H COOH
391
392 393O
O
H
OH
O
O
OHO
OH
H COOH
H
OH
H
OH
O
O
OHO
OH
H COOH
394OH
H
O
O
OHO
OH
H COOH
395OH
OH
H
OH
O
O
396OH
OH
O
COOH
OH
H
H
OH
O
O
OH
O
COOH
OH
H
O
O
397
26
HO
O
401
OH HOOH
O
O
R2
R1H
H O
O
O
H
HCOOH
398 R1 = OH R2 = CH3400 R1 = H R2 = CH2OCH3
Cl
O
H
H O
O
O
H
HCOOH
399
27
3.2 O-ether linkage (compounds 402416)
O
O
O
O
HO
O
O
H
408
O
O
H
H
H
HO
HOH
H
O
HH
H
H
O
409
O
O
H
H
H
HO
HOH
H
H H
410
HO
OH
H
HO
HOO
O
OH
HH
OH
H
HH H
411
O
O
O
OH
R
412 R = H413 R = H
O
O
O
O
O
O
OH
R
414 R =H415 R = H
OH
O
OEt
O
OO
OH
O
O
OO
O
O
O
OH405
O
OHC
O
OHO
H
R
406 R = H407 R = H
HO
O
OHC OH
OAc
OAc
O
OH
OO
#416
H
H
12'
OH
HOO
OH
OH
OH
OOH
OH
HO
402
403
HO
O
404
OH HOOH
28
3.3 Nitrogen and urea linkage (compounds 417427)
417
O
O
O
O
O
O
HN
H HN
O
H
H
H
H
HO
OH
H
HHH
OH
418
NH
N
O
H
HNH
O
COOMe
419
NH
O
HHN
H
420
HO
O
NHH
NH
O
421
N
OH
O
NH
OH H
NH
OOMe
R
422 R = H427 R = H
O
NHH
HNH
N
O COOMe
425
N
OH
O
NH
OH H
NH
ONHCH2CH2Ph
R
423 R= H426 R= OH
N
O
NH
OH H
NH
OOMe
424
29
3.4 Isocitric acid linkage (compounds 428437)
HHO
O
MeOOC
COOR3
O
HO
O
MeOOCCOOR1
COOR2#428 R1 = Me R2 = R3 = H429 R1 = H R2 = R3 = Me430 R2 = H R1 = R3 =Me
HHO
O
MeOOC
COOR1
O
HO
O
MeOOCCOOR2
COOR1431 R1 = H R2 = Me432 R1 = Me R2 = Me433 R1 = H R2 = H
HHO
O
R1OOC
COOH
O
HO
O
HOOCCOOR2
COOH434 R1 = Me R2 = Me435 R1 = H R2 = Me436 R1 = H R2 = H
COOMeCOOH
HH
COOMeCOOMe
H H
O
O
437
HH
OO
OO
30
3.5 Others (compounds 438447)
O
O
H
OH
H
438 O
COOMeOAc
O
O
O
AngO
O
O
O
OH
O
439
O
OH
O
ORO OH
O
OHOHO
OH
OO
HOHO
OO
HOO
HO
OOHOH
O
O
OH
O
R1O OH
O
OHOHO
OH
HOO
HOHO
OO
OO
HO
OOHOH
O
R2
445 R1 = Bz R2 = OH R3 = H446 R1 = p-Hpa R2 + R3 = O
447 R = p-Hpa
O
H
H
O
N
O
H
H O
H
HO
H
H
440
O
HOH
O
HOH
O O
HOHO
O
O
O O
HOHO
O
H
O
H OH
O
HOH
O
441
442
443
R3
444
OBz
OBz
31
4 Merosesquiterpenoid dimers
O
N
HHO
O
HO
O
N
HOH
O
OH( )n
448 n = 2449 n = 3
O
O
HHO
HO
O
N
HOH
O
OH
450
O
HHO
HO
O
HOH
OH
451 R1 =OH R2 =H452 R1 = OH R2 = H
R1
OOH
R2
O
H
R1
HO
453 R1 = OH R2 = H454 R1 = OAc R2 = H455 R1 = OH R2 = OH
HO O
H
OH
OH
R2O
O
OH
O
H
HOO
OH
O
H
H
457
H
OH
H
O
O
NHH H
OH
458
O
O
OH H
OH
459
O
O
NHH H
OH
460
O
O
NHH H
OH
461
O
O
H
O
H
462
OH
O
N
OH
HO
O
HOOC
O
OH
N
O
OH
#456
32
O
O
OH
OH
A
O
OH
R2
472 R1 = C R2 = H473 R1 = H R2 = C
HO
OH
OR
OH
HOO
R
O
474 R = A
O
O
O
O
RHO
OHO
R
475 R = A 3R476 R = A 3S
3A
R1
OH
R2
O
HO OR1
OH
R
O
O
HO
OH
R O
OH
R1
O
O
O
OH
R2
470 R = B 471 R1 = A R2 = C
R
B R = HC R = OH
469 R1 = A R2 = B
H
H
O
HO
H
O
OH
463
HO
O
O
R1
O
OHH
O
R2H
464 R1 = A R2 = OH465 R1 = A R2 = H
HO
O
O
R
O
OHH
O
466 R = A
H
HO R
O
OHH
467 R = A
O
OH
MeOOC
O
O
H
HH
H
H
H H
CHO
OH
H
HO
HO
O
O
468
H
33
N
HOHHOOC
N
HHO COOH
N
HOHHOOC
N
HHO COOH
477 478
HN
HOHHOOC
N
HO COOH
479
H
