4-butyl-2-methyl-5-oxo-(2S,3S,4S)-tetrahydro-3-furanyl 3-methylbutanoate | 110612-44-7

• 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,4S)-tetrahydro-3-furanyl 3-methylbutanoate
• 英文别名: epi-blastmycinone；α-n-Butyl-β-isovaleryloxy-γ-valerolakton；[(2S,3S,4S)-4-butyl-2-methyl-5-oxooxolan-3-yl] 3-methylbutanoate
• CAS: 110612-44-7
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: PCOOFQWEKVUBNN-GMXVVIOVSA-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：

  4-benzyloxy-(Z,4S)-2-penten-1-ol 在 palladium dihydroxide 、 4 A molecular sieve 咪唑 、 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 sodium chlorite 、 copper(l) iodide 、 过氧化氢异丙苯 、 氢气 、 双氧水 、 sodium acetate 、 sodium hydride 、 对甲苯磺酸 、 (-)-diethyl tartrate 、 pyridinium chlorochromate 作用下， 以 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 418.5h， 生成 4-butyl-2-methyl-5-oxo-(2S,3S,4S)-tetrahydro-3-furanyl 3-methylbutanoate
  参考文献：
  名称：

  三取代 γ-丁内酯立体选择性合成的灵活简单路线：(+)-芽生霉素及其类似物的全合成

  摘要：

  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。

  DOI：

  10.1055/s-2004-829173

文献信息

• [2 + 2] cycloaddition of optically active ketenes. Synthesis of (−)-blastmycinone. Preliminary Communication
  作者：Georg Fráter、Urs Müller、Wulf Günther

  DOI：10.1002/hlca.19860690813

  日期：1986.12.10

  [2 + 2] Cycloaddition of (menthyloxy)methylketene (2) to cis-ethyl propenyl ether showed a ca. 3:1 diastereo-selectivity. A two-step transformation of the thermodynamically more stable adduct 4 furnished the (2R*, 3R*)-compound 5 with ca. 50% e.e. (Scheme 1). The analogous reaction sequence with cis- benzyl 1-hexenyl ether (9) and 2 showed a ca. 5:1 diastereoselectivity in 10 and 11 (Scheme 2). Absolute

  [2 + 2]（薄荷基氧基）甲基乙烯酮（2）与顺式-乙基丙烯基醚的环加成反应显示为ca。3：1非对映选择性。热力学上更稳定的加合物4的两步转化使（2 R *，3 R *）化合物5的分子量约为1。50％ee（方案1）。与顺式-苄基1-己烯基醚（9）和2的类似反应序列显示出约1 。10和11中的5：1非对映选择性（方案2）。在C（3）和C（4）的绝对构型11（ - ） - blastmycinone已经通过将其转换到证明。因此，优选的过渡状态被推导为15。
• Total Syntheses of (−)-Grandinolide and (−)-Sapranthin by the Sharpless Asymmetric Dihydroxylation of Methyltrans-3-Pentenoate: Elucidation of the Stereostructure of (−)-Sapranthin
  作者：Christian Harcken、Reinhard Brückner、Elisabeth Rank

  DOI：10.1002/(sici)1521-3765(19981102)4:11<2342::aid-chem2342>3.0.co;2-q

  日期：1998.11.2

  Methyl trans-3-pentenoate (7) was converted into the cis-substituted gamma-lactone 8 in a single step with 78 % ee. The derived enolate dilithio-8 was alkylated trans-selectively with primary iodoalkanes. with 1-iodobutane dilithio-8 afforded, after esterification with isovaleroyl chloride, the epi-blast mycinone 9, Dilithio-8 gave (-)-grandinolide (11) with 1-iodo-19-phenylnonadecane (20), A third trans-selective alkylation of dilithio-8 was undertaken with 16-iodo-1.5-hexadecadiene-7,9-diyne (21). This gave the gamma-lactone 12. which had the published relative configuration of (-)-sapranthin but different spectroscopic data, When the OH group of lactone 8 was inverted (to hydroxylactone 40) and the derived enolate dilithio-40 alkylated with iodide 21, lactone 41 resulted, Its H-1 and C-13 NMR spectra and the sign and value of optical rotation coincide with the data of natural sapranthin, These findings establish that (-)-sapranthin possesses the relative and absolute configuration of stereoformula 41. The synthesis of iodide 21 was performed via the dienoic carboxylic ester trans-23 which stemmed from the Claisen-Ireland rearrangement (27 --> 28/29)/esterification (28/29 --> 26)/Cope rearrangement (26 - 23) sequence shown in Scheme 5.
• Synthesis of Optically Active Butenolides andγ-Lactones by the Sharpless Asymmetric Dihydroxylation ofβ,γ-Unsaturated Carboxylic Esters
  作者：Christian Harcken、Reinhard Brückner

  DOI：10.1002/anie.199727501

  日期：1997.1.7
• 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.