(2S,3R,4R,SR)-methyl 5-(p-tolylsulfinyl)-2,3-bis(benzyloxy)-4-hydroxypentanoate | 872168-01-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3R,4R,SR)-methyl 5-(p-tolylsulfinyl)-2,3-bis(benzyloxy)-4-hydroxypentanoate
• 英文别名: methyl (2S,3R,4R)-4-hydroxy-5-[(R)-(4-methylphenyl)sulfinyl]-2,3-bis(phenylmethoxy)pentanoate
• CAS: 872168-01-9
• 化学式: C₂₇H₃₀O₆S
• 分子量: 482.598
• InChiKey: OCZWGCFTMUYWDB-QZCKSCMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2S,3R,4R,SR)-methyl 5-(p-tolylsulfinyl)-2,3-bis(benzyloxy)-4-hydroxypentanoate 在 三氟化硼乙醚 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 13.5h， 生成 (2S,3R,4R,SR)-2,3-bis-benzyloxy-4-hydroxy-1-phenyl-5-(p-tolylsulfinyl)-pentan-1-one
  参考文献：
  名称：

  Total Stereoselective Synthesis of (+)-Goniothalesdiol

  摘要：

  The stereoselective synthesis of (+)-goniothalesdiol (1) was accomplished in nine steps starting from commercially available (-)-(2S,3s)dimethyl D-tartrate (3). The key features were a completely diastereoselective reduction of beta-ketosulfoxide to generate the stereogenic center at C-5 in 7 and formation of the 2,5-cis-substituted tetrahydrofuran ring in 10 from a stereoselective Et3SiH/TMSOTf-promoted reductive cyclization/ deoxygenation.

  DOI：

  10.1021/ol0523603
• 作为产物：
  描述：

  (R)-(+)-甲基对甲苯砜 在 zinc dibromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 生成 (2S,3R,4R,SR)-methyl 5-(p-tolylsulfinyl)-2,3-bis(benzyloxy)-4-hydroxypentanoate
  参考文献：
  名称：

  Total Stereoselective Synthesis of (+)-Goniothalesdiol

  摘要：

  The stereoselective synthesis of (+)-goniothalesdiol (1) was accomplished in nine steps starting from commercially available (-)-(2S,3s)dimethyl D-tartrate (3). The key features were a completely diastereoselective reduction of beta-ketosulfoxide to generate the stereogenic center at C-5 in 7 and formation of the 2,5-cis-substituted tetrahydrofuran ring in 10 from a stereoselective Et3SiH/TMSOTf-promoted reductive cyclization/ deoxygenation.

  DOI：

  10.1021/ol0523603

文献信息

• The Effect of Sulfoxides on the Stereoselective Construction of Tetrahydrofurans: Total Synthesis of (+)-Goniothalesdiol
  作者：Gloria Hernández-Torres、M. Carmen Carreño、Antonio Urbano、Françoise Colobert

  DOI：10.1002/chem.201002637

  日期：2011.1.24

  Good to excellent stereoselectivities were achieved in the reductive cyclization (with Et3SiH/trimethylsilyl trifluoromethanesulfonate (TMSOTf)) of enantiopure hydroxy sulfinyl ketones en route to 2,5‐cis‐disubstituted tetrahydrofuran skeletons. Electrostatic effects of the exocyclic sulfoxide, which stabilized the reactive intermediate oxocarbenium conformations, were responsible for the observed

  对映体纯的羟基亚磺酰基酮在2,5-顺式-二取代的四氢呋喃骨架的还原环化反应中（用Et 3 SiH /三甲基甲硅烷基三氟甲磺酸盐（TMSOTf））达到了良好的立体选择性。环外亚砜的静电作用使反应性中间体氧碳鎓构象稳定，这是观察到的立体控制的原因。提出了一个模型来解释结果。使用该反应和不对称还原β-酮亚砜作为关键步骤，促进了天然β-C-芳基糖苷（+）-goniothalesdiol的全部对映选择性合成。