(2SR,3RS,4RS)-methyl 5-O-benzyl-2,4-dimethyl-3,5-dihydroxypentanoate

• 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: (2SR,3RS,4RS)-methyl 5-O-benzyl-2,4-dimethyl-3,5-dihydroxypentanoate
• 英文别名: methyl (2S,3R,4R)-3-hydroxy-2,4-dimethyl-5-phenylmethoxypentanoate
• 化学式: C₁₅H₂₂O₄
• 分子量: 266.337
• InChiKey: DGBBPVPNSNTFJG-MBNYWOFBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2SR,3RS,4RS)-methyl 5-O-benzyl-2,4-dimethyl-3,5-dihydroxypentanoate 在 lithium aluminium tetrahydride 、 草酰氯 、 三氟甲磺酸 、 二甲基亚砜 作用下， 以 四氢呋喃 、 二氯甲烷 、 环己烷 为溶剂， 反应 0.5h， 生成 (2R,3S,4S)-3,5-bis(benzyloxy)-2,4-dimethylpentanal
  参考文献：
  名称：

  Diastereoselective Mukaiyama and Free Radical Processes for the Synthesis of Polypropionate Units

  摘要：

  Reported herein is the synthesis of 8 out of 16 polypropionates derived from our propionate units. A new strategy involving a stereoselective Mukaiyama aldol reaction followed by a stereoselective free-radical-based hydrogen transfer, both under Lewis acid control, is used. Of particular interest is the remarkable reactivity of (i-PrO)TiCl3 in this context to give only the 3,4-anti bromoesters.

  DOI：

  10.1021/ol049086h
• 作为产物：
  描述：

  (RS)-3-苄氧基-2-甲基丙醛 在 三氟甲磺酸二丁硼 、 sodium methylate 、 N,N-二异丙基乙胺 作用下， 反应 1.83h， 生成 (2SR,3RS,4RS)-methyl 5-O-benzyl-2,4-dimethyl-3,5-dihydroxypentanoate
  参考文献：
  名称：

  Studies in macrolide synthesis: an efficient synthesis of two chiral fragments of erythronolide a

  摘要：

  DOI：

  10.1016/s0040-4039(00)86280-2

文献信息

• Stereoselective total synthesis of (.+-.)-invictolide. An efficient preparation of a trisubstituted .delta.-lactone from aldol precursors
  作者：Ronaldo Aloise Pilli、Maria Marcia Murta

  DOI：10.1021/jo00054a014

  日期：1993.1

  The stereoselective total synthesis of (+/-)-invictolide (1), a component of the queen recognition pheromone of Solenopsis invicta, is described. The TiCl4-mediated addition of silyl ketene thioacetal 8 to (+/-)-3-(benzyloxy)-2-methylpropionaldehyde afforded exclusively thioester 10, in 65% yield, which was straightforwardly converted to diol 5 (ca. 31% yield). Diol 5 was also prepared after LiAlH4 reduction of the major aldol formed in the condensation between the lithium enolate of 2,6-di-tert-butyl-4-methylphenyl propanoate and (+/-)-2-methylvaleraldehyde (ca.50% overall yield). Intramolecular alkylation (t-BuOK-THF) of 6 or 7 gave a 40:60 mixture of (+/-)-1 and its C(3) epimer. Catalytic hydrogenation of unsaturated lactone 17 afforded (+/-)-1 in 80% yield.
• A Study of Exocyclic Radical Reductions of Polysubstituted Tetrahydropyrans
  作者：François Godin、Michel Prévost、Frédérick Viens、Philippe Mochirian、Jean-François Brazeau、Serge I. Gorelsky、Yvan Guindon

  DOI：10.1021/jo400721e

  日期：2013.6.21

  Exocyclic radical reductions were thoroughly investigated in the context of the synthesis of polysubstituted tetrahydropyrans, Which are found in numerous macrolides. The radical precursors studied herein were generated by tandem cycloetherification and iodoetherification reactions or, alternatively, by semicyclic acetals substitutions. DFT calculations (BHandHLYP/TZVP) performed at the transition-state level for the hydrogen radical delivery are in good accordance with the experimental data and enabled the identification of important conformational factors that govern the selectivities obtained. This study demonstrates:that both the preferred reactive conformation of the radical and steric interactions with the incoming hydride have to be considered in order to fully rationalize the levels of diastereoselection generated in acyclic free-radical processes.
• Studies in macrolide synthesis: an efficient synthesis of two chiral fragments of erythronolide a
  作者：Ian Paterson、Shailesh K Patel、John R. Porter

  DOI：10.1016/s0040-4039(00)86280-2

  日期：1983.1
• Diastereoselective Mukaiyama and Free Radical Processes for the Synthesis of Polypropionate Units
  作者：Yvan Guindon、Jean-François Brazeau

  DOI：10.1021/ol049086h

  日期：2004.7.1

  Reported herein is the synthesis of 8 out of 16 polypropionates derived from our propionate units. A new strategy involving a stereoselective Mukaiyama aldol reaction followed by a stereoselective free-radical-based hydrogen transfer, both under Lewis acid control, is used. Of particular interest is the remarkable reactivity of (i-PrO)TiCl3 in this context to give only the 3,4-anti bromoesters.