phenyl α-benzyloxythioacetate | 144192-68-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 英文名称: phenyl α-benzyloxythioacetate
• 英文别名: S-phenyl α-benzyloxythiopropionate；S-phenyl (phenylmethoxy)thioacetate；Ethanethioic acid, (phenylmethoxy)-, S-phenyl ester；S-phenyl 2-phenylmethoxyethanethioate
• CAS: 144192-68-7
• 化学式: C₁₅H₁₄O₂S
• 分子量: 258.341
• InChiKey: BLMSHQNHPDBMAP-UHFFFAOYSA-N

物化性质

• 沸点：
  378.3±25.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  phenyl α-benzyloxythioacetate 在 lithium aluminium tetrahydride 、 boron - (-)-menthone reagent 、 三乙胺 作用下， 反应 15.0h， 生成 (1S,2R) 1,3-dibenzoyloxy-2-benzyloxy-1-phenylpropane
  参考文献：
  名称：

  A highly enantio- and diastereoselective aldol reaction for α-heterosubstituted thioacetates

  摘要：

  Boron enolates derived from alpha-heterosubstituted thioacetates and bearing menthone-derived chiral ligands react with aldehydes to give anti aldols with excellent diastero- and enantiocontrol.

  DOI：

  10.1016/s0040-4039(00)76987-5
• 作为产物：
  描述：

  苄氧乙酸 、 苯硫酚 在 4-二甲氨基吡啶 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以94%的产率得到phenyl α-benzyloxythioacetate
  参考文献：
  名称：

  A Facile and Efficient Direct Aldol Addition of Simple Thioesters

  摘要：

  Simple thioesters undergo direct aldol addition to aldehydes in the presence of MgBr2.OEt2 and i-Pr2NEt using untreated, reagent-grade CH2Cl2 under atmospheric conditions. The reactions proceed extremely rapidly and in excellent yield.

  DOI：

  10.1021/ol060413q

文献信息

• Highly enantio- and diastereoselective boron aldol reactions of α-heterosubstituted thioacetates with aldehydes and silyl imines
  作者：Cesare Gennari、Anna Vulpetti、Gilles Pain

  DOI：10.1016/s0040-4020(97)00251-2

  日期：1997.4

  Boron enolates derived from α-heterosubstituted thioacetates and bearing menthone-derived chiral ligands react with aldehydes to give anti aldols with excellent diastero- and enantiocontrol. Boron enolates derived from tert-butyl α-halothioacetate and bearing menthone-derived chiral ligands react with imines with excellent diastero- and enantiocontrol to give syn α-halo-β-aminothioesters, which can

  衍生自α-杂取代硫代乙酸酯的硼烯酸酯和带有薄荷酮的手性配体与醛反应生成具有出色的非对映异构和对映异构控制的抗羟醛。衍生自α-卤代硫代乙酸叔丁酯并带有薄荷酮的手性配体的硼烯醇盐与亚胺反应，具有优异的非对映和对映体控制能力，可生成合成α-卤代-β-氨基硫酯，可通过在闭环过程中进行简单的闭环反应将其转化为相应的氮丙啶减少LAH。合成了抗菌素（+）-噻吩酚和（-）-氟苯尼考的​​关键前体。
• A Practical Synthesis of β-Keto Thioesters by Direct Crossed-Claisen Coupling of Thioesters and N-Acylbenzotriazoles
  作者：Don Coltart、Guoqiang Zhou、Daniel Lim、Fang Fang

  DOI：10.1055/s-0029-1216971

  日期：2009.10

  Thioesters undergo chemoselective soft enolization and acylation with N-acylbenzotriazoles on treatment with MgBr2˙OEt2 and i-Pr2NEt to give β-keto thioesters. Prior enolate formation is not required and the reaction is conducted using untreated dichloromethane open to the air.

  在MgBr2·OEt2和i-Pr2NEt处理下，硫酯通过化学选择性软烯醇化和N-酰基苯并三氮唑酰化，生成β-酮硫酯。无需先形成烯醇盐，反应在未经处理的二氯甲烷中进行，且对空气开放。
• Direct Carbon−Carbon Bond Formation via Chemoselective Soft Enolization of Thioesters: A Remarkably Simple and Versatile Crossed-Claisen Reaction Applied to the Synthesis of LY294002
  作者：Guoqiang Zhou、Daniel Lim、Don M. Coltart

  DOI：10.1021/ol801498u

  日期：2008.9.1

  Thioesters undergo chemoselective soft enolization and acylation by N-acylbenzotriazoles on treatment with MgBr(2)center dot OEt(2) and i-Pr(2)NEt to give beta-keto thioesters. Prior enolate formation is not required, and the reaction is conducted using untreated CH(2)Cl(2) open to the air. The coupled products are stable synthetic equivalents of beta-keto acids and can be converted directly into beta-keto esters, beta-keto amides, and beta-diketones under mild conditions. The utility of this carbon-carbon bond-forming method is shown through the synthesis of the PI3-K inhibitor LY294002.
• Diastereoselective synthesis of anti and syn .alpha.,.beta.-dihydroxy thioesters by titanium enolate aldol condensation
  作者：Rita Annunziata、Mauro Cinquini、Franco Cozzi、Andrea Lombardi Borgia

  DOI：10.1021/jo00049a053

  日期：1992.11
• Gennari Cesare, Vulpetti Anna, Moresca Daniela, Tetrahedron Lett, 35 (1994) N 27, S 4857-4860
  作者：Gennari Cesare, Vulpetti Anna, Moresca Daniela

  DOI：——

  日期：——