Methyl (2R,3R,4S)-<5-oxo-4-(phenylthio)-2-propyltetrahydrofuran-3-yl>acetate | 134829-40-6

• 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 (2R,3R,4S)-<5-oxo-4-(phenylthio)-2-propyltetrahydrofuran-3-yl>acetate
• 英文别名: methyl 2-((2R,3R,4S)-5-oxo-4-(phenylthio)-2-propyl-tetrahydrofuran-3-yl)acetate；methyl 2-((2R,3R,4S)-5-oxo-4-(phenylthio)-2-propyltetrahydrofuran-3-yl)acetate；methyl 2-[(2R,3R,4S)-5-oxo-4-phenylsulfanyl-2-propyloxolan-3-yl]acetate
• CAS: 134829-40-6
• 化学式: C₁₆H₂₀O₄S
• 分子量: 308.398
• InChiKey: MNTDSKPOFVPYNP-NFAWXSAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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 (2R,3R,4S)-<5-oxo-4-(phenylthio)-2-propyltetrahydrofuran-3-yl>acetate 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以96%的产率得到Methyl (2R,3R,4S)-<4-(benzenesulfinyl)-5-oxo-2-propyltetrahydrofuran-3-yl>acetate
  参考文献：
  名称：

  Stereoselective Synthesis of Highly Substituted .gamma.-Lactones and Butenolides by Intramolecular Michael Addition of Enantiomerically Enriched .gamma.-[(Phenylthio)acyl]oxy .alpha.,.beta.-Unsaturated Esters

  摘要：

  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.

  DOI：

  10.1021/jo00095a022
• 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 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 5.5h， 生成 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

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。
• An example of a chiral non-racemic carbanion as versatile synthon in the asymmetric synthesis of polysubstituted γ-lactones
  作者：Carmen Ma Rodríguez、Miguel A. Ramírez、Victor S. Martín

  DOI：10.1016/s0040-4039(00)79594-3

  日期：1992.5

  The application of a chiral non-racemic carbanion generated from enantiomerically enriched α-sulfonyl-γ-lactones to the asymmetric synthesis of highly substituted and fused γ-lactones is described.

  描述了由对映异构体富集的α-磺酰基-γ-内酯产生的手性非外消旋碳负离子在高度取代和稠合的γ-内酯的不对称合成中的应用。
• 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.
• γ-Lactones α,β- and β,γ-fused to carbocycles as novel antiproliferative drugs
  作者：Leticia G. León、Rubén P. Machín、Carmen M. Rodríguez、José L. Ravelo、Víctor S. Martín、José M. Padrón

  DOI：10.1016/j.bmcl.2008.08.098

  日期：2008.10

  A set of gamma-lactones alpha,beta-fused and beta,gamma-fused to carbocycles have been synthesized and evaluated for their in vitro antiproliferative activities using the human cancer cell lines SW1573 (lung), T-47D (breast) and WiDr (colon). The compounds are obtained by intramolecular ring closing metathesis of the corresponding dienes. Active compounds exhibited GI(50) values in the range 8-18 mu M. A structure-activity relationship is also discussed. (C) 2008 Elsevier Ltd. All rights reserved.
• Stereoselective Synthesis of Highly Substituted .gamma.-Lactones by Diastereoselective Alkylation of .alpha.-(Benzenesulfonyl) Derivatives with Unusual Facial Selectivity
  作者：Carmen M. Rodriquez、Tomas Martin、Miguel A. Ramirez、Victor S. Martin

  DOI：10.1021/jo00105a027

  日期：1994.12

  The oxidation of alpha-(phenylthio) gamma-lactones obtained by the base-induced cyclization of enantiomerically enriched gamma-[(phenylthio) acyl]-alpha,beta-unsaturated esters to sulfones in those cases where the a-carbon has an available proton and further basic alkylation led to an unexpected facial selectivity. The reaction proceeded smoothly with alkylating agents and unsaturated carbonyl compounds, but was unsuccessful when an addition to carbonyl derivatives was attempted. The alkylation reaction was performed over a wide range of substituted substrates in order to investigate the scope and limitations of the method and to have information about the possible origin of the selectivity. The application of the alkylation reaction was extended to the synthesis of bicyclic systems, including a cyclobutane with total stereochemical control. The presence of the alpha-(benzenesulfonyl) group is shown to be essential to achieve the facial selection. In order to rationalize the stereochemical results, extensive semiempirical calculations were performed. The use of MNDO and AM1 permits rationalization of the fact that the alpha-(benzenesulfonyl) group encumbers a diastereoface of the enolate generated in the ring, leading to the observed stereochemistry.