4-butyl-2-methyl-5-oxo-(2S,3S,4R)-tetrahydro-3-furanyl 3-methylbutanoate | 56271-03-5

• 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: 4-butyl-2-methyl-5-oxo-(2S,3S,4R)-tetrahydro-3-furanyl 3-methylbutanoate
• 英文别名: (-)-4-epi-blastomycinone；(-)-3-epi-blastmycinone；3-epi-blastmycinone；(-)-epi-blastomycinone；α-n-Butyl-β-isovaleryloxy-γ-valerolakton；[(2S,3S,4R)-4-butyl-2-methyl-5-oxooxolan-3-yl] 3-methylbutanoate
• CAS: 56271-03-5
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: PCOOFQWEKVUBNN-DMDPSCGWSA-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：

  己酸甲酯 在 rhodium on alumina 盐酸 、 4-二甲氨基吡啶 、 正丁基锂 、 氢气 、 对甲苯磺酸 、 二异丙胺 作用下， 以 四氢呋喃 、 吡啶 、 六甲基磷酰三胺 、 正己烷 、 乙酸乙酯 、 苯 为溶剂， -98.0~30.0 ℃ 、539.33 kPa 条件下， 反应 157.0h， 生成 4-butyl-2-methyl-5-oxo-(2S,3S,4R)-tetrahydro-3-furanyl 3-methylbutanoate
  参考文献：
  名称：

  （+）-blastcincinone和相关γ-内酯的总不对称合成

  摘要：

  通过使用容易获得的无C 2手性助剂（SMP或RMP），在四氢苯甲酸的α-位引入烷基取代基来实现构象异构体的冻结，并进行了所需的不对称γ-甲基化。它可用于（+）-blastmycinone（1）和（-）-3-epi-blastmycinone（2）的快速总合成，以及（+）-（3R，4R，5R）-4-的首次总合成描述了乙酰氧基-5-甲基-3-十四烷基四氢-2（5H）-呋喃酮（3）。

  DOI：

  10.1016/s0040-4020(01)85556-3

文献信息

• Flexible and Simple Route for the Stereoselective Synthesis of Trisubstituted γ-Butyrolactones: Total Synthesis of (+)-Blastomycinone and its Analogs
  作者：Palakodety Radha Krishna、V. V. Reddy、G. V. Sharma

  DOI：10.1055/s-2004-829173

  日期：——

  A flexible route for the stereoselective synthesis of trisubstituted γ-butyrolactones, namely (+)-blastomycinone and its analogs, is devised by the Sharpless asymmetric epoxidation and the regioselective ring opening reaction with dibutylcopper lithium as the key steps to introduce the requisite alkyl chain.

  通过 Sharpless 不对称环氧化和与二丁基铜锂的区域选择性开环反应作为引入所需烷基链的关键步骤，设计了一种灵活的立体选择性合成三取代 γ-丁内酯（即 (+)-blastomycinone 及其类似物）的路线。
• 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。
• Asymmetric synthesis of (−)-epi-blastmycinone and (2R,3S,4S)-3-hydroxy-4-methyl-2-(1′-n-tetradecyl)-butanolide via a tungsten-mediated cyclization reaction
  作者：Bo Liu、Ming-Jung Chen、Ching-Yu Lo、Rai-Shung Liu

  DOI：10.1016/s0040-4039(01)00189-7

  日期：2001.3

  Enantiocontrolled syntheses of the natural lactones 1 and 2 were achieved based on a tungsten-mediated cyclization. The whole syntheses comprise of six or seven steps from readily available 1-trimethylsilyl-pent-1-yne; the overall yields are 25 and 28% for 1 and 2, respectively. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Nishide, Kiyoharu; Aramata, Atsunori; Kamanaka, Teruki, Heterocycles, 1993, vol. 36, # 10, p. 2237 - 2240
  作者：Nishide, Kiyoharu、Aramata, Atsunori、Kamanaka, Teruki、Node, Manabu

  DOI：——

  日期：——
• 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.