1107-天然产物及逆合成分析与合成
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H
H
H
H
I
H CO2Me
OH
H CO2Me
H
MeO2C
+
MeO2C
MeO2C
O
H CO2Me
Synthesis of Veticadinol, Tietze(1998)
MeO2C
+
MeO2C O
0.1 eq. 醋酸哌啶盐 CH2Cl2, 20 oC 82%
CO2Me MeO2C
citronellal 香茅醛;玫瑰醛;3,7-二甲基-6-辛烯醛
CO2Me HO CO2Me
TsCl, 吡啶, 0-5 oC 93%
TsO CO2Me
H
NaI, 丙酮, 20 oC 95%
I CO2Me
H
LDA THF, -78 oC -20 oC 92%
H CO2Me
3eq. MeMgCl 乙醚， rt 77%
OH H
Veticadinol, 8 steps total yield: 36%
Some Famous Natural Compounds
H2NOC H2NOC N H N H2NOC CN N
CONH2 CONH2
Co +
N
Vitamin B12
O NH N N HO O
-
CONH2
O P O
O OH
C63H88CoN14O14P Exact Mass: 1354.57 Mol. Wt.: 1355.37 C, 55.83; H, 6.54; Co, 4.35; N, 14.47; O, 16.53; P, 2.29
O O O OH
O N H OH
O O OH OBz O H O O
(-)-Taxol C47H51NO14 Exact Mass: 853.33 Mol. Wt.: 853.91 C, 66.11; H, 6.02; N, 1.64; O, 26.23
Veticadinol
H
H
OH
Retrosynthetic Analysis
O O O H OH N O O O H
OTBS O H O
HO
O
O OH
FK-1012 C108H174N4O30Si2 Exact Mass: 2063.18 Mol. Wt.: 2064.72 C, 62.82; H, 8.49; N, 2.71; O, 23.25; Si, 2.72
OH O O OH O HO
O
O O O H O O OH N O O O OH H O H O
OH
FK-506 C44H69NO13 Exact Mass: 819.48 Mol. Wt.: 820.02 C, 64.45; H, 8.48; N, 1.71; OBiblioteka Baidu 25.36
O O N O H O O H H N O H N O O OTBS O OH O H O O O O
FeCl3/Al2O3 CH2Cl2, -78-20 oC 92%
CO2Me MeO2C
+
MeO2C
98.8:1.2
CO2Me
NaCl, H2O, DMSO 150 oC 92%
CO2Me
Synthesis of Veticadinol, Tietze(1998)
(CH2O)n, 1 eq. AlMe2Cl CH2Cl2, 0 to 20 oC 81%
OH
OH OH
O OH HO NH2 OH OH O HO N H N H O OH HO OH O OH OH H HO OH OH OH
OH
OH
OH OH OH O OH OH
OH OH
HO O HO H OH OH OH OH
O
O
OH OH O OH HO OH OH OH
Palytoxin
C129H223N3O54 Exact Mass: 2678.48 Mol. Wt.: 2680.14 C, 57.81; H, 8.39; N, 1.57; O, 32.24
H
H
H
I
H CO2Me
OH
H CO2Me
H
MeO2C
+
MeO2C
MeO2C
O
H CO2Me
Synthesis of Veticadinol, Tietze(1998)
MeO2C
+
MeO2C O
0.1 eq. 醋酸哌啶盐 CH2Cl2, 20 oC 82%
CO2Me MeO2C
citronellal 香茅醛;玫瑰醛;3,7-二甲基-6-辛烯醛
CO2Me HO CO2Me
TsCl, 吡啶, 0-5 oC 93%
TsO CO2Me
H
NaI, 丙酮, 20 oC 95%
I CO2Me
H
LDA THF, -78 oC -20 oC 92%
H CO2Me
3eq. MeMgCl 乙醚， rt 77%
OH H
Veticadinol, 8 steps total yield: 36%
Some Famous Natural Compounds
H2NOC H2NOC N H N H2NOC CN N
CONH2 CONH2
Co +
N
Vitamin B12
O NH N N HO O
-
CONH2
O P O
O OH
C63H88CoN14O14P Exact Mass: 1354.57 Mol. Wt.: 1355.37 C, 55.83; H, 6.54; Co, 4.35; N, 14.47; O, 16.53; P, 2.29
O O O OH
O N H OH
O O OH OBz O H O O
(-)-Taxol C47H51NO14 Exact Mass: 853.33 Mol. Wt.: 853.91 C, 66.11; H, 6.02; N, 1.64; O, 26.23
Veticadinol
H
H
OH
Retrosynthetic Analysis
O O O H OH N O O O H
OTBS O H O
HO
O
O OH
FK-1012 C108H174N4O30Si2 Exact Mass: 2063.18 Mol. Wt.: 2064.72 C, 62.82; H, 8.49; N, 2.71; O, 23.25; Si, 2.72
OH O O OH O HO
O
O O O H O O OH N O O O OH H O H O
OH
FK-506 C44H69NO13 Exact Mass: 819.48 Mol. Wt.: 820.02 C, 64.45; H, 8.48; N, 1.71; OBiblioteka Baidu 25.36
O O N O H O O H H N O H N O O OTBS O OH O H O O O O
FeCl3/Al2O3 CH2Cl2, -78-20 oC 92%
CO2Me MeO2C
+
MeO2C
98.8:1.2
CO2Me
NaCl, H2O, DMSO 150 oC 92%
CO2Me
Synthesis of Veticadinol, Tietze(1998)
(CH2O)n, 1 eq. AlMe2Cl CH2Cl2, 0 to 20 oC 81%
OH
OH OH
O OH HO NH2 OH OH O HO N H N H O OH HO OH O OH OH H HO OH OH OH
OH
OH
OH OH OH O OH OH
OH OH
HO O HO H OH OH OH OH
O
O
OH OH O OH HO OH OH OH
Palytoxin
C129H223N3O54 Exact Mass: 2678.48 Mol. Wt.: 2680.14 C, 57.81; H, 8.39; N, 1.57; O, 32.24