(S)-4-benzyl-3-octanoyloxazolidin-2-one | 152899-13-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (S)-4-benzyl-3-octanoyloxazolidin-2-one
• 英文别名: (4S)-4-benzyl-3-octanoyl-1,3-oxazolidin-2-one
• CAS: 152899-13-3
• 化学式: C₁₈H₂₅NO₃
• 分子量: 303.401
• InChiKey: WSEQNPPQOAHUGX-INIZCTEOSA-N

物化性质

• 沸点：
  454.3±14.0 °C(Predicted)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-4-benzyl-3-octanoyloxazolidin-2-one 在 lithium hydroxide 、 正丁基锂 、 双氧水 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 11.5h， 生成 (S)-4-苄基-3-丙酰基-2-噁唑烷酮
  参考文献：
  名称：

  Total synthesis and structure assignment of the antitumor antibiotic aranorosin

  摘要：

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.

  DOI：

  10.1021/jo00077a050
• 作为产物：
  描述：

  (S)-4-苄基-3-丙酰基-2-噁唑烷酮 在 lithium hydroxide 、 正丁基锂 、 双氧水 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 11.5h， 生成 (S)-4-benzyl-3-octanoyloxazolidin-2-one
  参考文献：
  名称：

  Total synthesis and structure assignment of the antitumor antibiotic aranorosin

  摘要：

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.

  DOI：

  10.1021/jo00077a050

文献信息

• Understanding Programming of Fungal Iterative Polyketide Synthases: The Biochemical Basis for Regioselectivity by the Methyltransferase Domain in the Lovastatin Megasynthase
  作者：Ralph A. Cacho、Justin Thuss、Wei Xu、Randy Sanichar、Zhizeng Gao、Allison Nguyen、John C. Vederas、Yi Tang

  DOI：10.1021/jacs.5b11814

  日期：2015.12.23

  Highly reducing polyketide synthases (HR-PKSs) from fungi synthesize complex natural products using a single set of domains in a highly programmed, iterative fashion. The most enigmatic feature of HR-PKSs is how tailoring domains function selectively during different iterations of chain elongation to afford structural diversity. Using the lovastatin nonaketide synthase LovB as a model system and a

  来自真菌的高度还原性聚酮化合物合酶 (HR-PKS) 以高度程序化的迭代方式使用一组域合成复杂的天然产物。HR-PKS 最神秘的特征是在链伸长的不同迭代过程中，剪裁域如何有选择地发挥作用，以提供结构多样性。使用洛伐他汀九肽合酶 LovB 作为模型系统和各种酰基底物，我们表征了 LovB 甲基转移酶 (MT) 域的底物特异性。我们表明，虽然 MT 结构域对不同的 β-酮酰基基团显示出甲基化活性，但在链长和功能化方面，它对其自然编程的 β-酮-二烯基四酮底物具有异常选择性。伴随酮还原酶 (KR) 结构域的表征显示出对不同 β-酮酰基基团更广泛的底物特异性。我们的研究表明，相对于其他竞争域的转化率，通过对特定底物的更高动力学效率来实现通过定制域（例如 MT）进行的选择性修饰。
• The total synthesis of the diepoxycyclohexanone antibiotic aranorosin and novel synthetic analogues
  作者：Alexander McKillop、Lee McLaren、Richard J. K. Taylor、Robert J. Watson、Norman J. Lewis

  DOI：10.1039/p19960001385

  日期：——

  A short synthesis of the novel antibiotic aranorosin in chiral form is described which employs (i) a novel hypervalent iodine-mediated oxidative hydroxylation of a tyrosinal derivative and (ii) a stereocontrolled cis-bisepoxidation in the key steps. A similar procedure was employed to prepare 6′-epiaranorosin, and hence establish the stereochemistry of the natural compound, and to prepare novel aranorosin

  描述了手性形式的新型抗生素阿糖胞苷的简短合成，其在关键步骤中采用了（i）酪氨酸衍生物的新型高价碘介导的氧化羟基化作用和（ii）立体控制的顺式-双环氧化。采用相似的方法制备6'-表皮阿糖胞苷，从而建立天然化合物的立体化学，并制备新的阿糖胞苷类似物。描述了一种有机金属路线，该路线产生了脱酰胺基芳族松香。
• Isolation and total synthesis of gymnastatin N, a POLO-like kinase 1 active constituent from the fungus Arachniotus punctatus
  作者：Chee Wee Phoon、Brinda Somanadhan、Sabrina Cher Hui Heng、Anna Ngo、Siew Bee Ng、Mark S. Butler、Antony D. Buss、Mui Mui Sim

  DOI：10.1016/j.tet.2004.09.046

  日期：2004.12

  as a minor component. Gymnastatin N (1) was found to be a 52:48 mixture of (1S,6′R) and (1R,6′R) diastereomers, by synthesis of the four possible diastereomers and comparison of the optical rotation and chiral HPLC profile of each diastereoisomer with the natural product. Analogues of 1 were synthesized and evaluated against the Plk1 assay and these SAR studies suggested that the diene and free carboxylic

  针对POLO样激酶1（Plk1）（一种抗癌靶标）的高通量筛选，鉴定了一种来自点状真菌Arachniotus punctatus的活性提取物。生物测定指导的分馏导致分离出新的天然产物gymaststatin N（1）和已知的化合物阿诺洛糖醇A（2），IC 50值分别为13和118μM 。分离出金格他汀N，3的12'-羟基类似物作为次要成分。Gymnastatin N（1）被认为是（1的52:48混合物小号，6' - [R ）和（1 - [R，6' - [R）非对映异构体，可以合成四种可能的非对映异构体，并比较每种非对映异构体与天然产物的旋光度和手性HPLC谱。合成了类似物1并针对Plk1分析进行了评估，这些SAR研究表明，二烯和游离羧酸部分可能是其生物活性的原因。
• Volatile Methyl Esters of Medium Chain Length from the Bacterium Chitinophaga Fx7914
  作者：Thorben Nawrath、Klaus Gerth、Rolf Müller、Stefan Schulz

  DOI：10.1002/cbdv.201000190

  日期：——

  The analysis of the volatiles released by the novel bacterial isolate Chitinophaga Fx7914 revealed the presence of ca. 200 compounds including different methyl esters. These esters comprise monomethyl- and dimethyl-branched, saturated, and unsaturated fatty acid methyl esters that have not been described as bacterial volatiles before. More than 30 esters of medium C-chain length were identified, which

  对新型细菌分离物Chitinophaga Fx7914释放的挥发物的分析表明存在ca。200种化合物，包括不同的甲酯。这些酯包含以前从未被描述为细菌挥发物的单甲基和二甲基支化的，饱和和不饱和的脂肪酸甲酯。鉴定出30多种中等C链长度的酯，它们属于5个主要类别，即（S）-2-甲基链烷酸甲酯（A类），（S）-2甲基，（ω-1）-二甲基链烷酸甲酯（B类） ），2，（ω-2）-二甲基链烷酸甲酯（C类），（E）-2-甲基烷-2-烯酸甲酯（D类）和甲基（E）-2，（ω-1）-二甲基烷- 2-烯酸酯（E类）。通过GC / MS分析和目标化合物的合成验证了化合物的结构，即目标化合物为（S）-2-甲基辛酸甲酯（28），（S）-2,7-二甲基辛酸甲酯（（S）-43），2,6-二甲基辛酸甲酯（49），（E）-2-甲基壬-2-烯酸甲酯（20a）和（E）-2,7-二甲基辛-2-烯酸甲酯（41a）。此外，如通过使用手性相的GC
• The Revised Structure, Total Synthesis, and Absolute Configuration of Streptophenazine A
  作者：Zhicai Yang、Xiaomin Jin、Michael Guaciaro、Bruce F. Molino、Ursula Mocek、Ricardo Reategui、Joshua Rhea、Tim Morley

  DOI：10.1021/ol202005u

  日期：2011.10.21

  A total synthesis of both diastereomers of the originally proposed structure for streptophenazine A (1) has been achieved. However, both synthetic compounds are different from the natural product. Re-examination of NMR data reported for streptophenazine A and a concise total synthesis of both diastereomers of 17 (17a and 17b) led to the structural revision of streptophenazine A to 17b. Asymmetric synthesis

  已完全合成了链霉菌素A（1）最初提出的结构的两种非对映异构体。但是，两种合成化合物均不同于天然产物。报告的链脲吩嗪A的NMR数据的重新检查以及17个非对映异构体（17a和17b）的简明全合成导致链脲吩嗪A的结构修订为17b。还进行了（-）-链霉吩嗪A的不对称合成，其绝对构型确定为1 'S，2'R。