(2R,5R)-2-<(1R)-1-<(tert-Butyldimethylsilyl)oxy>tridecyl>-5-<(1R)-1-hydroxy-3-butynyl>tetrahydrofuran | 161615-42-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: (2R,5R)-2-<(1R)-1-<(tert-Butyldimethylsilyl)oxy>tridecyl>-5-<(1R)-1-hydroxy-3-butynyl>tetrahydrofuran
• 英文别名: (2R,5R,1'R,1"R)-2-(1'-hydroxy-3'-butynyl)-5-<1"-(tert-butyldimethylsilyl)oxytridecyl>tetrahydrofuran；(1R)-1-[(2R,5R)-5-[(1R)-1-[tert-butyl(dimethyl)silyl]oxytridecyl]oxolan-2-yl]but-3-yn-1-ol
• CAS: 161615-42-5
• 化学式: C₂₇H₅₂O₃Si
• 分子量: 452.794
• InChiKey: OBPQMEKFWCCQBP-VEYUFSJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.62
• 重原子数：
  31
• 可旋转键数：
  17
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,5R)-2-<(1R)-1-<(tert-Butyldimethylsilyl)oxy>tridecyl>-5-<(1R)-1-hydroxy-3-butynyl>tetrahydrofuran 在 咪唑 、 正丁基锂 、 三氟化硼乙醚 、 氢氟酸 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 54.33h， 生成 (2S)-4-[(8R,13R)-8-hydroxy-13-(methoxymethoxy)-13-[(2R,5R)-5-[(1R)-1-(methoxymethoxy)tridecyl]oxolan-2-yl]tridec-10-ynyl]-2-methyl-2H-furan-5-one
  参考文献：
  名称：

  Total Synthesis of (10R)- and (10S)-Corossolin:  Determination of the Stereochemistry at C-10 of the Natural Corossolin and the Differential Toxicity toward Cancer Cells Caused by the Configuration at C-10

  摘要：

  (10R)和(10S)-corossolin是通过将炔烃中间体18分别与环氧27或29发生偶联反应而合成的。将两种人工合成的corossolin的物理数据与天然corossolin的已报道数据进行对比后发现，天然corossolin在C-10位的构型极有可能是R型。在初步的体外实验中，R型异构体对B16BL6细胞系的抑制活性是S型异构体的18倍。

  DOI：

  10.1021/jo982241j
• 作为产物：
  描述：

  (3R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-1-oxiranyl-hexadecan-3-ol 在 草酰氯 、 camphor-10-sulfonic acid 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (2R,5R)-2-<(1R)-1-<(tert-Butyldimethylsilyl)oxy>tridecyl>-5-<(1R)-1-hydroxy-3-butynyl>tetrahydrofuran
  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

• Diastereoselective Propargylation of .alpha.-Alkoxy Aldehydes with Propargyl Bromide and Zinc. A Versatile and Efficient Method for the Synthesis of Chiral Oxygenated Acyclic Natural Products
  作者：Wen-Lian Wu、Zhu-Jun Yao、Yun-Long Li、Jin-Cui Li、Yi Xia、Yu-Lin Wu

  DOI：10.1021/jo00115a049

  日期：1995.5