(3S,5R)-5-(tert-butyldiphenylsilyloxymethyl)-3-methyl-dihydrofuran-2(3H)-one | 147200-08-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S,5R)-5-(tert-butyldiphenylsilyloxymethyl)-3-methyl-dihydrofuran-2(3H)-one
• 英文别名: (3S,5R)-5-(tert-butyldiphenylsilyloxymethyl)-3-methyldihydrofuran-2(3H)-one；3S,5R-5-(t-butyldiphenylsiloxymethyl)-3-methyl-4,5-dihydro-2(3H)-furanone；(3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-methyloxolan-2-one
• CAS: 147200-08-6
• 化学式: C₂₂H₂₈O₃Si
• 分子量: 368.548
• InChiKey: XBHGPYCZPIKCFG-ZWKOTPCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,5R)-5-(tert-butyldiphenylsilyloxymethyl)-3-methyl-dihydrofuran-2(3H)-one 在 三甲基铝 、 Di-tert-butylpyridine 作用下， 以 二氯甲烷 为溶剂， 生成 (2S,4R)-5-[tert-butyl(diphenyl)silyl]oxy-N,4-dimethoxy-N,2-dimethylpentanamide
  参考文献：
  名称：

  Synthesis of the C1–C27 portion of the aplyronines

  摘要：

  This manuscript describes the use of the anti,anti-diastereoselective aldol reaction of an efficiently generated dipropionate equivalent to construct the C-5-C-14-portion of the aplyronines. This portion was then coupled with a compound corresponding to C-15-G(20) of the targets. Further elaboration and an additional coupling led to an intermediate containing C-1-C-27 with appropriate stereochemistry and functionalization for eventual conversion into the aplyronines. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.04.159
• 作为产物：
  描述：

  D-谷氨酸 在 咪唑 、 dimethyl sulfide borane 、 lithium diisopropyl amide 、 sodium nitrite 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (3S,5R)-5-(tert-butyldiphenylsilyloxymethyl)-3-methyl-dihydrofuran-2(3H)-one
  参考文献：
  名称：

  zoanthamine / norzoanthamine生物碱的合成研究：杂环胺核心的高级中间体

  摘要：

  以对映体和立体选择性的方式制备了先进的中间体，用于制备藏菊胺基间氮杂胺生物碱的杂环氨基核。利用立体选择性铜酸盐添加到容易获得的（+）-Wieland-Miescher酮中，选择性地构建连续的四元手性中心。

  DOI：

  10.1016/s0040-4039(98)01284-2

文献信息

• Enantioselective Total Synthesis of (+)-Ophiobolin A
  作者：Kazuhiro Tsuna、Naoyoshi Noguchi、Masahisa Nakada

  DOI：10.1002/chem.201204119

  日期：2013.4.22

  The enantioselective total synthesis of (+)‐ophiobolin A is described. This total synthesis features the construction of the spiro CD ring of (+)‐ophiobolin A through a stereoselective intramolecular Hosomi–Sakurai cyclization reaction, the joining of the A ring to the CD ring by using a reaction reported by Utimoto, and the construction of the ophiobolin eight‐membered carbocyclic ring through ring‐closing

  描述了（+）-ophiobolin A的对映选择性全合成。这种全合成的特征是通过立体选择性分子内Hosomi-Sakurai环化反应来构建（+）-ophiobolin A的螺旋CD环，利用Utimoto报道的反应将A环连接至CD环，以及构建ophiobolin通过闭环复分解（RCM）进行的八元碳环，这是本研究中首次进行。该成功的RCM反应需要使用在C5位含有苄氧基或甲氧基甲氧基且在C6位含有异丙烯基或其羟基化形式的底物。
• Design, synthesis, and cytotoxicity of stabilized mycolactone analogs
  作者：Vaddela Sudheer Babu、Ya Zhou、Yoshito Kishi

  DOI：10.1016/j.bmcl.2017.01.036

  日期：2017.3

  On exposure to visible light, mycolactone A/B, the causative toxin of Buruli ulcer, rearranges to a mixture of four photo-mycolactones apparently via a rare photochemically-induced [4πs + 2πa] cycloaddition. In order to prevent the rearrangement, two C6′-C7′ dihydromycolactone analogs 6′α-15 and 6′β-15 were designed and synthesized. 6′α-15 and 6′β-15 were shown to be stable under not only photochemical

  上经由罕见光化学诱导的[明显暴露于可见光，细菌内酯A / B，布鲁里溃疡的致病毒素，重排的四个光电-mycolactones混合物4个π小号 +  2 π一个]环加成。为了防止重排，设计并合成了两个C6'-C7'二氢霉菌内酯类似物6'α- 15和6'β- 15。6′α- 15和6′β- 15不仅在光化学条件下，而且在酸性和碱性条件下均显示稳定。测试了针对任意选择的四种细胞系（人Hek-293，人肺癌A-549，人黑素瘤LOX-IMVI和小鼠L-929）的细胞毒性，从而揭示：（1）两种类似物均保持有效的细胞毒性；（2）6'β- 15对人类细胞系的效力显着高于6'α- 15；（3）与亲本支链内酯A / B相比，6'β- 15对人Hek-293表现出相同的效力，而对人肺癌A-549和人黑素瘤LOX-IMVI的效力明显较低。
• Different Modes of Cyclization in Zoanthamine Alkaloid System, Bisaminal versus Spiroketal Formation
  作者：Takahiro Nakajima、Daisuke Yamashita、Kaname Suzuki、Atsuo Nakazaki、Takahiro Suzuki、Susumu Kobayashi

  DOI：10.1021/ol200486c

  日期：2011.6.17

  Bisaminal cyclization in the zoanthamine alkaloid system was strongly affected by the stereochemistry of the C4 methyl. While cyclization of the (4S)-methyl precursor gave only a bisaminal compound, cyclization of the (4R)-methyl isomer produced both spiroketal and bisaminal products.

  zoanthamine生物碱系统中的双氨基苯环化受到C4甲基的立体化学的强烈影响。虽然（4S）-甲基前体的环化仅产生双氨醛化合物，但（4R）-甲基异构体的环化产生螺缩醛和双氨醛产品。
• Total Synthesis of (−)‐Norzoanthamine
  作者：Daisuke Yamashita、Yoshihisa Murata、Naotsuka Hikage、Ken‐ichi Takao、Atsuo Nakazaki、Susumu Kobayashi

  DOI：10.1002/anie.200804546

  日期：2009.2.9

  No bones about it: (−)‐Norzoanthamine, a promising candidate for an anti‐osteoporotic drug, was the target of a total synthesis (see scheme). The final bisaminal formation with AcOH/H2O gave the DEFG ring, while the cyclization precursor was prepared by installing the remaining bisaminal unit after oxidative cleavage of the cyclopentanol moiety.

  毫无保留：（-）-去甲蒽胺是抗骨质疏松药物的有希望的候选者，是总合成的目标（请参阅方案）。最终用AcOH / H 2 O形成的双氨醛形成DEFG环，而环化前体是通过在环戊醇部分的氧化裂解后安装剩余的双氨醛单元而制备的。
• Synthetic Studies on (+)-Ophiobolin A:  Asymmetric Synthesis of the Spirocyclic CD-Ring Moiety
  作者：Naoyoshi Noguchi、Masahisa Nakada

  DOI：10.1021/ol060437x

  日期：2006.5.1

  Asymmetric synthesis of the spirocyclic CID-ring moiety of (+)-ophiobolin A is described. Fragment A, which was prepared via pig liver esterase (PLE)-mediated kinetic resolution, and fragment B, which was prepared via diastereoselective allylation and subsequent kinetic iodolactonization, were coupled to afford the allylsilane 2, which was successfully cyclized to the desired spirocyclic CD-ring moiety la in the presence of a Lewis acid.