(2R,3S,4S)-3,5-bis(benzyloxy)-2,4-dimethylpentanal | 479196-93-5

• 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: (2R,3S,4S)-3,5-bis(benzyloxy)-2,4-dimethylpentanal
• 英文别名: (2R,3S,4S)-2,4-dimethyl-3,5-bis(phenylmethoxy)pentanal
• CAS: 479196-93-5
• 化学式: C₂₁H₂₆O₃
• 分子量: 326.436
• InChiKey: AEOMWHIIQMSPLH-BBTUJRGHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S)-3,5-bis(benzyloxy)-2,4-dimethylpentanal 在 Ti(OiPr)Cl3 、 三氟甲磺酸二丁硼 、 氢气 、 N,N-二异丙基乙胺 、 palladium dichloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 9.25h， 生成 (+/-)-(3R,4R,5S,6S)-4-hydroxy-6-((S)-1-hydroxyprop-2-yl)-3,5-dimethyltetrahydropyran-2-one
  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：

  2,2,2-三氯乙酰胺苄酯 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

文献信息

• Stereopentads Derived from a Sequence of Mukaiyama Aldolization and Free Radical Reduction on α-Methyl-β-alkoxy Aldehydes: A General Strategy for Efficient Polypropionate Synthesis
  作者：Jean-François Brazeau、Philippe Mochirian、Michel Prévost、Yvan Guindon

  DOI：10.1021/jo8021583

  日期：2009.1.2

  aldolization with enoxysilane 24 followed by a hydrogen transfer reaction. Recent advancements concerning these reactions are described, and novel key intermediates are characterized in the aldol step. The synthesis of C(1)−C(11) fragment 60 of zincophorin, which contains a synthetically challenging stereopentad unit, is described attesting the usefulness of our strategy.

  在一个stereodivergent方式，所有非对映体16个stereopentads 7 - 22合成起始α甲基β -烷氧基醛25和27。我们设计了一种方法，该方法基于先用乙氧基硅烷24进行Mukaiyama醛缩醛缩合反应，然后进行氢转移反应。描述了有关这些反应的最新进展，并在醇醛步骤中表征了新的关键中间体。描述了锌卟啉的C（1）-C（11）片段60的合成，其中包含一个具有挑战性的立体五单元，证明了我们策略的有效性。
• Total synthesis of zincophorin methyl ester. Stereocontrol of 1,2-induction using sterically hindered enoxysilanes
  作者：François Godin、Philippe Mochirian、Gabrielle St-Pierre、Yvan Guindon

  DOI：10.1016/j.tet.2014.11.061

  日期：2015.1

  Reported herein is the total synthesis of zincophorin methyl ester, a polyketide ionophore. Of particular interest is the use of sterically hindered nucleophiles to surmount the unfavorable stereochemical outcome, leading to acetate aldol adducts, in nucleophilic addition to the aldehyde derived from propionates. The approach is based on the addition of an enoxysilane (bearing a removable phenylselenide

  本文报道的是聚酮化物离子载体锌卟啉甲酯的全合成。特别令人感兴趣的是，在向丙酸酯衍生的醛的亲核加成中，使用空间位阻亲核试剂来克服不利的立体化学结果，导致乙酸羟醛加合物。该方法基于添加环氧乙烷（带有可移动的苯基硒化物部分）以在BF 3 OEt 2介导的Mukaiyama醛醇缩合反应中选择性生成Felkin-Anh加合物。随后硒化物基团的还原导致相应的乙酸顺式-羟醛基序，并且该方法被用于选择性地诱导锌卟啉的C12–C13关系。
• Further studies on chromium(II)-mediated homoallylic alcohol syntheses
  作者：Michael D. Lewis、Yoshito Kishi

  DOI：10.1016/s0040-4039(00)87337-2

  日期：1982.1

  The stereochemical outcome of chromium(II)-mediated syntheses of homoallylic alcohols has been examined on 11 aldehydes, – .

  铬（II）高烯丙醇的合成介导的立体化学结果已经检查了11种醛，- 。
• 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.