(+/-)-epi-blastmycinone | 53494-50-1

• 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: (+/-)-epi-blastmycinone
• 英文别名: 2-Epiblastmycinone；[(2R,3S,4R)-4-butyl-2-methyl-5-oxooxolan-3-yl] 3-methylbutanoate
• CAS: 53494-50-1
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: PCOOFQWEKVUBNN-NQBHXWOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  S-tert-Butyl (2R^*,3S^*)-2-butyl-3-hydroxy-5-(trimethylsilyl)-4-pentynethioate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 thallium(III) nitrate 、 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 32.0h， 生成 (+/-)-epi-blastmycinone
  参考文献：
  名称：

  High diastereoselective aldol reactions of cobalt-complexed and uncomplexed propynals with an O-silyl ketene O,S-acetal: highly stereoselective total syntheses of (.+-.)-blastmycinone and its three diastereoisomers from 3-(trimethylsilyl)propynal

  摘要：

  Total syntheses of (+/-)-blastmycinone (2) and its three diastereoisomers (3-5) are described. The syntheses involve highly stereoselective aldol reactions of cobalt-complexed propynal 6 and uncomplexed propynal 7 with O-silyl ketene O,S-acetal 8, which possesses an n-butyl tether, under Mukaiyama conditions. (+/-)-Blastmycinone (2) and its 2-epimer 3 were stereoselectively synthesized through chelation-controlled reduction, whereas (+/-)-3-epi- and 4-epiblastmycinone (5 and 4) were obtained in a highly stereocontrolled manner with bromolactonization as a key step.

  DOI：

  10.1021/jo00063a008

文献信息

• Diastereofacial selection in nitrile oxide cycloaddition reactions. The anti-directing effect of an allylic oxygen and some new results on the ring metalation of isoxazolines. A synthesis of (.+-.)-blastmycinone
  作者：Alan P. Kozikowski、Arun K. Ghosh

  DOI：10.1021/jo00189a024

  日期：1984.7

  the adducts to known γ-lactones. The stereochemistry associated with the metalation/alkylation of 5-alkoxymethyl-substituted isoxazolines has also been probed in order to further expand the use of these heterocycles as aldol equivalents in natural products total synthesis. A synthesis of (±)-blastmycinone (34) is reported which combines the two foregoing aspects of stereocontrol. The levels of regio-

  已经研究了与腈氧化物与带有烯丙基氧取代基的烯烃的反应有关的非对映选择性的程度。当3-丁烯-2-醇（5）或（+）-（S）-异亚丙基-3-丁烯-1,2-二醇（1）的叔丁基二甲基甲硅烷基醚衍生物为1时，已发现合理的非对映选择性水平。用作双极亲虫。这些环加成反应的立体化学过程已通过将加合物转化为已知的γ-内酯的方法得到严格证明。还探索了与5-烷氧基甲基取代的异恶唑啉的金属化/烷基化有关的立体化学，以进一步扩展这些杂环作为天然产物总合成中的羟醛等效物的用途。据报道，（±）-blastcincinone（34）的合成结合了立体声控制的上述两个方面。还讨论了在由异亚丙基-D-甘油醛制得的顺式和反式二取代的烯烃35和39的环加成反应中发现的区域选择性和立体选择性。给出了手性烯烃与手性腈的反应的单个例子。
• Stereoselective additions to carboxylic acid dianions and β-lactone substituted ester enolates
  作者：Johann Mulzer、Peter De Lasalle、Alexander Chucholowski、Ursula Blaschek、Gisela Brüntrup、Ibrahim Jibril、Gottfried Huttner

  DOI：10.1016/0040-4020(84)80003-4

  日期：1984.1

  β-unsaturated β-hydroxy-carboxylic acids 2a/b. A diastereo- and enantioselective aldoltype addition of phenylacetic acid dianion to benzaldehyde has been achieved by employing optically active alkoxide amide bases. Finally, highly stereocontrolled additions to the novel β-lactone substituted ester enolates 22 are described.

  据报道，利用抗构型的γ，β-不饱和β-羟基羧酸2a / b，对于外消旋的4-表-blastmycinone（6）和δ-multistriatine（13）进行了新的立体选择性合成。通过使用旋光性醇盐酰胺碱，已将苯乙酸二阴离子非对映体和对映体选择性的醛醇型加成到苯甲醛中。最后，描述了对新型β-内酯取代的酯烯酸酯22的高度立体控制的加成。
• High diastereoselective aldol reactions of cobalt-complexed and uncomplexed propynals with an O-silyl ketene O,S-acetal: highly stereoselective total syntheses of (.+-.)-blastmycinone and its three diastereoisomers from 3-(trimethylsilyl)propynal
  作者：Chisato Mukai、Osamu Kataoka、Miyoji Hanaoka

  DOI：10.1021/jo00063a008

  日期：1993.5

  Total syntheses of (+/-)-blastmycinone (2) and its three diastereoisomers (3-5) are described. The syntheses involve highly stereoselective aldol reactions of cobalt-complexed propynal 6 and uncomplexed propynal 7 with O-silyl ketene O,S-acetal 8, which possesses an n-butyl tether, under Mukaiyama conditions. (+/-)-Blastmycinone (2) and its 2-epimer 3 were stereoselectively synthesized through chelation-controlled reduction, whereas (+/-)-3-epi- and 4-epiblastmycinone (5 and 4) were obtained in a highly stereocontrolled manner with bromolactonization as a key step.