Methyl (4R)-4-<(phenylthio)acetoxy>hept-2(E)-enoate | 134829-39-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Methyl (4R)-4-<(phenylthio)acetoxy>hept-2(E)-enoate
• 英文别名: methyl (4R)-4-[(phenylthio)-acetoxy]hept-2(E)-enoate；methyl (4R)-4-[(phenylthio)acetoxy]hept-2(E)-enoate；methyl (E,4R)-4-(2-phenylsulfanylacetyl)oxyhept-2-enoate
• CAS: 134829-39-3
• 化学式: C₁₆H₂₀O₄S
• 分子量: 308.398
• InChiKey: FSCRLUUHXBKQAC-OCHBPSSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl (4R)-4-<(phenylthio)acetoxy>hept-2(E)-enoate 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 以95%的产率得到Methyl (2R,3R,4S)-<5-oxo-4-(phenylthio)-2-propyltetrahydrofuran-3-yl>acetate
  参考文献：
  名称：

  γ-内酯系环闭合复分解。将对映体富集的γ-内酯α，β融合到中等大小的环上的途径。

  摘要：

  [反应：见正文]通过对映异构体富集的α-[（苯硫基）酰基]-α，β的碱诱导环化获得的α-（苯磺酰基）-β-[（甲氧羰基）甲基]-γ-内酯的立体选择性烷基化-不饱和酯和闭环烯烃复分解（RCM）是获得α，β融合至中型碳环和环醚的γ-内酯的新方法的基础。

  DOI：

  10.1021/ol0478739
• 作为产物：
  描述：

  苯硫基乙酸 在 titanium(IV) isopropylate 、 sodium periodate 、 水 、 sodium hydride 、 四丁基高碘酸铵 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 1.5h， 生成 Methyl (4R)-4-<(phenylthio)acetoxy>hept-2(E)-enoate
  参考文献：
  名称：

  γ-内酯系环闭合复分解。将对映体富集的γ-内酯α，β融合到中等大小的环上的途径。

  摘要：

  [反应：见正文]通过对映异构体富集的α-[（苯硫基）酰基]-α，β的碱诱导环化获得的α-（苯磺酰基）-β-[（甲氧羰基）甲基]-γ-内酯的立体选择性烷基化-不饱和酯和闭环烯烃复分解（RCM）是获得α，β融合至中型碳环和环醚的γ-内酯的新方法的基础。

  DOI：

  10.1021/ol0478739

文献信息

• γ-Lactone-Tethered Ring-Closing Metathesis. A Route to Enantiomerically Enriched γ-Lactones α,β-Fused to Medium-Sized Rings
  作者：Carmen M. Rodríguez、José Luis Ravelo、Víctor S. Martín

  DOI：10.1021/ol0478739

  日期：2004.12.1

  [reaction: see text] The stereoselective alkylation of alpha-(phenylsulfonyl)-beta-[(methoxycarbonyl)methyl]-gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched alpha-[(phenylthio)acyl]-alpha,beta-unsaturated esters and ring-closing olefin metathesis (RCM) are the basis of a new approach for gaining access to gamma-lactones that are alpha,beta-fused to medium-sized

  [反应：见正文]通过对映异构体富集的α-[（苯硫基）酰基]-α，β的碱诱导环化获得的α-（苯磺酰基）-β-[（甲氧羰基）甲基]-γ-内酯的立体选择性烷基化-不饱和酯和闭环烯烃复分解（RCM）是获得α，β融合至中型碳环和环醚的γ-内酯的新方法的基础。
• Stereoselective Synthesis of Highly Substituted .gamma.-Lactones and Butenolides by Intramolecular Michael Addition of Enantiomerically Enriched .gamma.-[(Phenylthio)acyl]oxy .alpha.,.beta.-Unsaturated Esters
  作者：Carmen M. Rodriguez、Tomas Martin、Miguel A. Ramirez、Victor S. Martin

  DOI：10.1021/jo00095a022

  日期：1994.8

  The synthesis of polysubstituted gamma-lactones by the base-induced cyclization of enantiomerically enriched gamma-((phenylthio)acyl)oxy alpha,beta-unsaturated esters obtained from 2,3-epoxy alcohols is described. The procedure is highly stereoselective and compatible with a wide range of functionalities (ester, tetrahydropyranyl ether, silyl ether, etc.). Varying degrees of substitution, including quaternary centers, in the final gamma-lactone were synthesized with excellent stereoselectivity. Useful functional interconversions were successfully demonstrated, in particular those resulting in butenolides. By the use of AM1 it was concluded that the intramolecular Michael reaction can be described as a kinetically controlled reaction in which the relative stability of the transition states for all possible final configurations led to geometries in agreement with the experimental results.
• An approach to the stereocontrolled synthesis of polysubstituted chiral butenolides and γ-lactones
  作者：Carmen Ma Rodríguez、Victor S. Martín

  DOI：10.1016/s0040-4039(00)71265-2

  日期：1991.5

  The enantioselective synthesis of polysubstituted butenolides and gamma-lactones by an intramolecular Michael addition of chiral thiophenylacetates of gamma-hydroxy-alpha,beta-unsaturated esters is described.
• Rodriguez Carmen M., Martin Tomas, Ramirez Miguel A., Martin iVictor S., J. Org. Chem, 59 (1994) N 16, S 4461-4472
  作者：Rodriguez Carmen M., Martin Tomas, Ramirez Miguel A., Martin iVictor S.

  DOI：——

  日期：——
• γ-Lactones as templates in ring-closing metathesis: Enantioselective synthesis of medium sized carbocycles fused to butyrolactones
  作者：José Luis Ravelo、Carmen Ma Rodríguez、Víctor S. Martín

  DOI：10.1016/j.jorganchem.2006.08.021

  日期：2006.12