(5S)-3-<8-Oxo-(13R)-13-<(tert-butyldimethylsilyl)oxy>-13-<(2R,5R)-tetrahydro-5-<(1R)-1-<(tert-butyldimethylsilyl)oxy>tridecyl>furan-2-yl>tridecyl>-5-methylfuran-2(5H)-one | 161615-48-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (5S)-3-<8-Oxo-(13R)-13-<(tert-butyldimethylsilyl)oxy>-13-<(2R,5R)-tetrahydro-5-<(1R)-1-<(tert-butyldimethylsilyl)oxy>tridecyl>furan-2-yl>tridecyl>-5-methylfuran-2(5H)-one
• 英文别名: (2S)-4-[(13R)-13-[tert-butyl(dimethyl)silyl]oxy-13-[(2R,5R)-5-[(1R)-1-[tert-butyl(dimethyl)silyl]oxytridecyl]oxolan-2-yl]-8-oxotridecyl]-2-methyl-2H-furan-5-one
• CAS: 161615-48-1
• 化学式: C₄₇H₉₀O₆Si₂
• 分子量: 807.399
• InChiKey: CXVHBVBQHRGSKM-FXJNEGIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.36
• 重原子数：
  55
• 可旋转键数：
  32
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (5S)-3-<8-Oxo-(13R)-13-<(tert-butyldimethylsilyl)oxy>-13-<(2R,5R)-tetrahydro-5-<(1R)-1-<(tert-butyldimethylsilyl)oxy>tridecyl>furan-2-yl>tridecyl>-5-methylfuran-2(5H)-one 在 氢氟酸 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 24.0h， 以83%的产率得到corossolone
  参考文献：
  名称：

  Synthetic Studies toward Mono-THF Annonaceous Acetogenins: A Diastereoselective and Convergent Approach to Corossolone and (10RS)-Corossoline

  摘要：

  This paper describes a diastereoselective approach to the total syntheses of both corossolone (1) and (10RS)-corossoline (2), two naturally occurring cytotoxic annonaceous acetogenins from Annona muricata. 2,3-O-Isopropylidene-D-threitol (3) has be en used as the chiral pool for the preparation of (5R,6R)-5-hydroxy-6-[(tert-butyldimethylsilyl)oxy]-1-octadecene (10). Epoxidation of 10 with m-CPBA and intramolecular ring closure in one pot gave a trans-THF intermediate 11 as the major product. The subsequent reagent-controlled asymmetric propargylation was achieved by treatment of the aldehyde derived from 11 with 2-allenyl-1,3,2-dioxaborolane-(4S,5S)-dicarboxylic acid bis-(1'-methylethyl) ester to afford compound 12 with the threo-trans-threo THF moiety with excellent diastereoselectivity. Epoxide 21 prepared from ethyl L-lactate and undecenoic acid according to our previous methodology was treated with alkynyl anion 13 derived from 12 in the presence of BF3-OEt(2) to give the regioselective ring-opening product 22 with the whole skeleton of the target molecule. Finally, beta-elimination followed by deprotection or by oxidation and then deprotection afforded corossolone and (10RS)-corossoline, whose physical data are coincident with those of the natural products.

  DOI：

  10.1021/jo00110a019
• 作为产物：
  描述：

  (2R,5R)-5-[(1R)-1-[tert-butyl(dimethyl)silyl]oxytridecyl]oxolane-2-carbaldehyde 在 palladium on activated charcoal 咪唑 、 正丁基锂 、 草酰氯 、 三氟化硼乙醚 、 氢气 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 47.08h， 生成 (5S)-3-<8-Oxo-(13R)-13-<(tert-butyldimethylsilyl)oxy>-13-<(2R,5R)-tetrahydro-5-<(1R)-1-<(tert-butyldimethylsilyl)oxy>tridecyl>furan-2-yl>tridecyl>-5-methylfuran-2(5H)-one
  参考文献：
  名称：

  Synthetic Studies toward Mono-THF Annonaceous Acetogenins: A Diastereoselective and Convergent Approach to Corossolone and (10RS)-Corossoline

  摘要：

  This paper describes a diastereoselective approach to the total syntheses of both corossolone (1) and (10RS)-corossoline (2), two naturally occurring cytotoxic annonaceous acetogenins from Annona muricata. 2,3-O-Isopropylidene-D-threitol (3) has be en used as the chiral pool for the preparation of (5R,6R)-5-hydroxy-6-[(tert-butyldimethylsilyl)oxy]-1-octadecene (10). Epoxidation of 10 with m-CPBA and intramolecular ring closure in one pot gave a trans-THF intermediate 11 as the major product. The subsequent reagent-controlled asymmetric propargylation was achieved by treatment of the aldehyde derived from 11 with 2-allenyl-1,3,2-dioxaborolane-(4S,5S)-dicarboxylic acid bis-(1'-methylethyl) ester to afford compound 12 with the threo-trans-threo THF moiety with excellent diastereoselectivity. Epoxide 21 prepared from ethyl L-lactate and undecenoic acid according to our previous methodology was treated with alkynyl anion 13 derived from 12 in the presence of BF3-OEt(2) to give the regioselective ring-opening product 22 with the whole skeleton of the target molecule. Finally, beta-elimination followed by deprotection or by oxidation and then deprotection afforded corossolone and (10RS)-corossoline, whose physical data are coincident with those of the natural products.

  DOI：

  10.1021/jo00110a019

文献信息

• Synthetic Studies toward Mono-THF Annonaceous Acetogenins: A Diastereoselective and Convergent Approach to Corossolone and (10RS)-Corossoline
  作者：Zhu-Jun Yao、Yu-Lin Wu

  DOI：10.1021/jo00110a019

  日期：1995.3

  This paper describes a diastereoselective approach to the total syntheses of both corossolone (1) and (10RS)-corossoline (2), two naturally occurring cytotoxic annonaceous acetogenins from Annona muricata. 2,3-O-Isopropylidene-D-threitol (3) has be en used as the chiral pool for the preparation of (5R,6R)-5-hydroxy-6-[(tert-butyldimethylsilyl)oxy]-1-octadecene (10). Epoxidation of 10 with m-CPBA and intramolecular ring closure in one pot gave a trans-THF intermediate 11 as the major product. The subsequent reagent-controlled asymmetric propargylation was achieved by treatment of the aldehyde derived from 11 with 2-allenyl-1,3,2-dioxaborolane-(4S,5S)-dicarboxylic acid bis-(1'-methylethyl) ester to afford compound 12 with the threo-trans-threo THF moiety with excellent diastereoselectivity. Epoxide 21 prepared from ethyl L-lactate and undecenoic acid according to our previous methodology was treated with alkynyl anion 13 derived from 12 in the presence of BF3-OEt(2) to give the regioselective ring-opening product 22 with the whole skeleton of the target molecule. Finally, beta-elimination followed by deprotection or by oxidation and then deprotection afforded corossolone and (10RS)-corossoline, whose physical data are coincident with those of the natural products.