首页分子通化学资讯化学百科反应查询关于我们

请输入关键词

历史搜索

热门化合物HOT

喹啉
水杨醛
二溴甲烷
谷胱甘肽
L-乳酸
苯巴比妥
辣椒碱
非那明
百草枯
联苯烯

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one | 474411-18-2

分子结构分类

有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类

中文名称

——

中文别名

——

英文名称

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one

英文别名

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanoxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-azabicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one化学式

CAS

474411-18-2

化学式

C₃₆H₅₉NO₈Si

mdl

——

分子量

661.952

InChiKey

HNGUKHSZEQCFGX-BAJCTEGPSA-N

BEILSTEIN

——

EINECS

——

物化性质

沸点：

733.1±60.0 °C(Predicted)
密度：

1.07±0.1 g/cm3(Predicted)

计算性质

辛醇/水分配系数(LogP)：

7.1
重原子数：

46.0
可旋转键数：

7.0
环数：

2.0
sp3杂化的碳原子比例：

0.64
拓扑面积：

104.71
氢给体数：

2.0
氢受体数：

8.0

上下游信息

上游原料

中文名称	英文名称	CAS号	化学式	分子量
——	(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-9-(triethyl-silanyloxy)-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one	474411-17-1	C₄₂H₇₃NO₈Si₂	776.215
——	(2E,4Z,6S,7S,8E,10S,11R,12S,14R)-15-(3-amino-2,5,6-trimethoxy-phenyl)-11-(tert-butyl-dimethyl-silanyloxy)-6,12-dimethoxy-2,8,10,14-tetramethyl-7-(triethyl-silanyloxy)-pentadeca-2,4,8-trienoic acid	474410-92-9	C₄₂H₇₅NO₉Si₂	794.23
——	(2E,4Z,6S,7S,8E,10S,11R,12S,14R)-15-(3-amino-2,5,6-trimethoxy-phenyl)-11-(tert-butyl-dimethyl-silanyloxy)-6,12-dimethoxy-2,8,10,14-tetramethyl-7-(triethyl-silanyloxy)-pentadeca-2,4,8-trienoic acid allyl ester	474411-16-0	C₄₅H₇₉NO₉Si₂	834.295
——	(2E,4Z,6S,7S,8E,10S,11R,12S,14R)-11-(tert-butyl-dimethyl-silanyloxy)-6,12-dimethoxy-15-(3-nitro-2,5,6-trimethoxy-phenyl)-2,8,10,14-tetramethyl-7-(triethyl-silanyloxy)-pentadeca-2,4,8-trienoic acid allyl ester	474411-03-5	C₄₅H₇₇NO₁₁Si₂	864.277
——	(2Z,4S,5S,6E,8S,9R,10S,12R)-9-((tert-butyldimethylsilyl)oxy)-4,10-dimethoxy-6,8,12-trimethyl-5-((triethylsilyl)oxy)-13-(2,3,6-trimethoxy-5-nitrophenyl)trideca-2,6-dienal	474411-15-9	C₃₉H₆₉NO₁₀Si₂	768.149
——	(2Z,4S,5S,6E,8S,9R,12R,10S)-9-(tert-butyl-dimethyl-silanyloxy)-4,10-dimethoxy-13-(3-nitro-2,5,6-trimethoxy-phenyl)-6,8,12-trimethyl-5-(triethyl-silanyloxy)-trideca-2,6-dien-1-ol	474411-14-8	C₃₉H₇₁NO₁₀Si₂	770.164
——	(E)-(2R,3S,6S,7R,8S,10R)-7-(tert-Butyl-dimethyl-silanyloxy)-2,8-dimethoxy-4,6,10-trimethyl-3-triethylsilanyloxy-11-(2,3,6-trimethoxy-5-nitro-phenyl)-undec-4-enal	625450-93-3	C₃₇H₆₇NO₁₀Si₂	742.111
——	(2R,3S,4E,6S,7R,8S,10R)-7-(tert-butyl-dimethyl-silanyloxy)-3-hydroxy-2,8-dimethoxy-11-(3-nitro-2,5,6-trimethoxy-phenyl)-4,6,10-trimethyl-undec-4-enoic acid methyl ester	474411-01-3	C₃₂H₅₅NO₁₁Si	657.874
——	(2E,4S,5R,6S,8R)-5-(tert-butyl-dimethyl-silanyloxy)-6-methoxy-9-(3-nitro-2,5,6-trimethoxy-phenyl)-2,4,8-trimethyl-non-2-enoic acid ethyl ester	474410-98-5	C₃₀H₅₁NO₉Si	597.822
——	(2E,4S,5R,6S,8R)-5-(tert-butyl-dimethyl-silanyloxy)-6-methoxy-9-(3-nitro-2,5,6-trimethoxy-phenyl)-2,4,8-trimethyl-non-2-en-1-ol	474411-21-7	C₂₈H₄₉NO₈Si	555.784
——	(2R,3S,4E,6S,7R,8S,10R)-7-(tert-butyl-dimethyl-silanyloxy)-2,8-dimethoxy-11-(3-nitro-2,5,6-trimethoxy-phenyl)-4,6,10-trimethyl-3-(triethyl-silanyloxy)-undec-4-enoic acid methyl ester	474411-13-7	C₃₈H₆₉NO₁₁Si₂	772.137
——	(2E,4S,5R,6S,8R)-5-(tert-butyl-dimethyl-silanyloxy)-6-methoxy-9-(3-nitro-2,5,6-trimethoxy-phenyl)-2,4,8-trimethyl-non-2-enal	474410-99-6	C₂₈H₄₇NO₈Si	553.769
——	(3R,4S,6R)-3-(tert-butyl-dimethyl-silanyloxy)-2,6-dimethyl-4-methoxy-7-(5-nitro-2,3,6-trimethoxy-phenyl)-hept-1-ene	474410-96-3	C₂₅H₄₃NO₇Si	497.704
——	(2S,3R,4S,6R)-2,6-dimethyl-4-methoxy-7-(5-nitro-2,3,6-trimethoxy-phenyl)-heptane-1,3-diol-1,3-bis-(tert-butyl-dimethyl-silyl) ether	474411-11-5	C₃₁H₅₉NO₈Si₂	629.982
——	(2S,3R,4S,6R)-3-(tert-butyl-dimethyl-silanyloxy)-2,6-dimethyl-4-methoxy-7-(5-nitro-2,3,6-trimethoxy-phenyl)-heptan-1-ol	474411-20-6	C₂₅H₄₅NO₈Si	515.72
——	(2R,3R,4S,6R)-3-(tert-Butyl-dimethyl-silanyloxy)-4-methoxy-2,6-dimethyl-7-(2,3,6-trimethoxy-5-nitro-phenyl)-heptanal	474411-12-6	C₂₅H₄₃NO₈Si	513.704
——	(3R,4S,6R)-3-(tert-butyl-dimethyl-silanyloxy)-4-methoxy-6-methyl-7-(5-nitro-2,3,6-trimethoxy-phenyl)-heptan-2-ol	474410-95-2	C₂₄H₄₃NO₈Si	501.693
——	(3R,4S,6R)-3-(tert-butyl-dimethyl-silanyloxy)-4-methoxy-6-methyl-7-(5-nitro-2,3,6-trimethoxy-phenyl)-heptan-2-one	474411-09-1	C₂₄H₄₁NO₈Si	499.677
——	(2R,3S,5R)-2-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-5-methyl-6-(5-nitro-2,3,6-trimethoxy-phenyl)-hexanal	474411-08-0	C₂₃H₃₉NO₈Si	485.65
——	(2R,3S,5R)-2-(tert-butyl-dimethyl-silanyloxy)-3-methoxy-5-methyl-6-(5-nitro-2,3,6-trimethoxy-phenyl)-hexanoic acid methyl ester	474410-94-1	C₂₄H₄₁NO₉Si	515.676
——	(2R,3S,4E,6S,7R,8S,10R)-7-(tert-butyl-dimethyl-silanyloxy)-3-hydroxy-2,8-dimethoxy-11-(3-nitro-2,5,6-trimethoxy-phenyl)-4,6,10-trimethyl-undec-4-enoic acid (1R,2S)-2-[benzyl-(2,4,6-trimethyl-benzenesulfonyl)-amino]-1-phenyl-propyl ester	474411-00-2	C₅₆H₈₀N₂O₁₃SSi	1049.41
——	(3R,4S,6R)-2,6-dimethyl-3-hydroxy-4-methoxy-7-(5-nitro-2,3,6-trimethoxy-phenyl)-hept-1-ene	474411-10-4	C₁₉H₂₉NO₇	383.442
——	(3S,5S,6S)-3-[(1S,3R)-1-methoxy-3-methyl-4-(5-nitro-2,3,6-trimethoxy-phenyl)-butyl]-5,6-bis-(4-methoxy-phenyl)-[1,4]dioxan-2-one	326606-26-2	C₃₃H₃₉NO₁₁	625.673
——	(3S,5S,6S)-3-[(1S,3R)-1-hydroxy-3-methyl-4-(5-nitro-2,3,6-trimethoxy-phenyl)-butyl]-5,6-bis-(4-methoxy-phenyl)-[1,4]dioxan-2-one	326606-16-0	C₃₂H₃₇NO₁₁	611.646
——	(2R,3S,5R)-2-[(1S,2S)-2-hydroxy-1,2-bis-(4-methoxy-phenyl)-ethoxy]-3-methoxy-5-methyl-6-(5-nitro-2,3,6-trimethoxy-phenyl)-hexanoic acid methyl ester	474410-93-0	C₃₄H₄₃NO₁₂	657.715
——	(2R,3S,5R)-2-hydroxy-3-methoxy-5-methyl-6-(5-nitro-2,3,6-trimethoxy-phenyl)-hexanoic acid methyl ester	474411-07-9	C₁₈H₂₇NO₉	401.414
——	(2S,3R,4S,6R)-2,6-dimethyl-4-methoxy-7-(5-nitro-2,3,6-trimethoxy-phenyl)-heptane-1,3-diol	474410-97-4	C₁₉H₃₁NO₈	401.457

下游产品

中文名称	英文名称	CAS号	化学式	分子量
——	(4E,6Z,8S,9S,10E,12S,13R,14S,16R) carbamic acid 13-(tert-butyl-dimethyl-silanyloxy)-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-3-oxo-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-9-yl ester	474411-19-3	C₃₇H₆₀N₂O₉Si	704.977
——	(4E,6Z,8S,9S,10E,12S,13R,14S,16R) carbamic acid 13-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-3-oxo-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-9-yl ester	474410-91-8	C₃₁H₄₆N₂O₉	590.714
——	tert-butyl (4E,6Z,8S,9S,10E,12S,13R,14S,16R)-9-[bis[(2-methylpropan-2-yl)oxycarbonyl]carbamoyloxy]-13-[tert-butyl(dimethyl)silyl]oxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-3-oxo-2-azabicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaene-2-carboxylate	625450-87-5	C₅₂H₈₄N₂O₁₅Si	1005.33
——	(4E,6Z,8S,9S,10E,12S,13R,14S,16R) carbamic acid 13-hydroxy-8,14,20,22-tetramethoxy-4,10,12,16-tetramethyl-3,19-dioxo-2-aza-bicyclo[16.3.1]docosa-1,4,6,10,18(22),20-hexaen-9-yl ester	474411-04-6	C₃₀H₄₂N₂O₉	574.671
格尔德霉素	geldanmycin	30562-34-6	C₂₉H₄₀N₂O₉	560.645

反应信息

作为反应物：

描述：

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one 在 silver(II) oxide 、氢氟酸、硝酸作用下，以 1,4-二氧六环、二氯甲烷、乙腈为溶剂，反应 8.75h，生成 (4E,6Z,8S,9S,10E,12S,13R,14S,16R) carbamic acid 13-hydroxy-8,14,20,22-tetramethoxy-4,10,12,16-tetramethyl-3,19-dioxo-2-aza-bicyclo[16.3.1]docosa-1,4,6,10,18(22),20-hexaen-9-yl ester

参考文献：

名称：

（+）-格尔德霉素和（-）-邻-喹戈德霉素的全合成：不对称乙醇酸酯羟醛反应和生物学评估。

摘要：

（+）-格尔德霉素（GA）的总合成遵循线性路线，最后一步是使用脱甲基醌形成反应完成的。关键步骤包括使用两个新的不对称乙醇酸硼酸羟醛缩醛反应。为了设定抗C11，12羟基甲氧基官能度，使用（S，S）-5，6-双-4-甲氧基苯基二恶烷酮8。衍生自去氧麻黄碱5的乙醇酸甲酯设置了C6,7甲氧基氨基甲酸酯的立体化学。与硝酸相比，使用硝酸的醌形成步骤得到的非天然邻-喹啉-GA产物55为10：1。其他已知的氧化剂产生了不寻常的氮杂醌产物49。o-Quino-GA 55以良好的亲和力结合Hsp90，但与GA相比，细胞毒性较小。

DOI：

10.1021/jo034870l
作为产物：

描述：

(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-9-(triethyl-silanyloxy)-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one 在四丁基氟化铵作用下，以四氢呋喃为溶剂，反应 4.5h，以90%的产率得到(4E,6Z,8S,9S,10E,12S,13R,14S,16R)-13-(tert-butyl-dimethyl-silanyloxy)-9-hydroxy-8,14,19,20,22-pentamethoxy-4,10,12,16-tetramethyl-2-aza-bicyclo[16.3.1]docosa-1(21),4,6,10,18(22),19-hexaen-3-one

参考文献：

名称：

（+）-格尔德霉素和（-）-邻-喹戈德霉素的全合成：不对称乙醇酸酯羟醛反应和生物学评估。

摘要：

（+）-格尔德霉素（GA）的总合成遵循线性路线，最后一步是使用脱甲基醌形成反应完成的。关键步骤包括使用两个新的不对称乙醇酸硼酸羟醛缩醛反应。为了设定抗C11，12羟基甲氧基官能度，使用（S，S）-5，6-双-4-甲氧基苯基二恶烷酮8。衍生自去氧麻黄碱5的乙醇酸甲酯设置了C6,7甲氧基氨基甲酸酯的立体化学。与硝酸相比，使用硝酸的醌形成步骤得到的非天然邻-喹啉-GA产物55为10：1。其他已知的氧化剂产生了不寻常的氮杂醌产物49。o-Quino-GA 55以良好的亲和力结合Hsp90，但与GA相比，细胞毒性较小。

DOI：

10.1021/jo034870l

点击查看最新优质反应信息

文献信息

Total Synthesis of (+)-Geldanamycin and (−)-o-Quinogeldanamycin with Use of Asymmetric Anti- and Syn-Glycolate Aldol Reactions

作者：Merritt B. Andrus、Erik L. Meredith、Bryon L. Simmons、B. B. V. Soma Sekhar、Erik J. Hicken

DOI：10.1021/ol0267432

日期：2002.10.1

Geldanamycin (GA), an antitumor Hsp90 inhibitor, was made for the first time by using an oxidative demethylation reaction as the final step. A biaryldioxanone auxiliary set the anti C11-12 hydroxy-methoxy functionality and a methylglycolate auxiliary based on norephedrine was used for the syn C6-7 methoxy-urethane. p-Quinone-forming oxidants, CAN and AgO, produced an unusual aza-quinone product. Nitric acid gave GA from a trimethoxy precursor in 55% yield as a 1:10 mixture with nonnatural o-quino-GA.