((2S,6R)-6-[2-(4-methoxybenzyloxy)ethyl]-4-methylenetetrahydropyran-2-yl)-acetaldehyde | 617714-87-1

• 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,6R)-6-[2-(4-methoxybenzyloxy)ethyl]-4-methylenetetrahydropyran-2-yl)-acetaldehyde
• 英文别名: 2-[(2S,6R)-6-[2-[(4-methoxyphenyl)methoxy]ethyl]-4-methylideneoxan-2-yl]acetaldehyde
• CAS: 617714-87-1
• 化学式: C₁₈H₂₄O₄
• 分子量: 304.386
• InChiKey: WUWMOMQZYKVIHK-MSOLQXFVSA-N

物化性质

• 沸点：
  428.9±40.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ((2S,6R)-6-[2-(4-methoxybenzyloxy)ethyl]-4-methylenetetrahydropyran-2-yl)-acetaldehyde 在 三溴化硼 、 (1R,2R)-N,N'-二-对-甲苯磺酰-1,2-二苯基-1,2-乙烯二胺 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 二氯甲烷 为溶剂， 反应 18.08h， 生成 (2R,5S)-8,8-Dimethoxy-1-{(2S,6R)-6-[2-(4-methoxy-benzyloxy)-ethyl]-4-methylene-tetrahydro-pyran-2-yl}-5-methyl-4-methylene-octan-2-ol
  参考文献：
  名称：

  二十碳五烯内酯A：第二代正式合成。

  摘要：

  （+）-Leucascandrolide A（1）的收敛的第二代正式合成已通过针对生物活性大内酯组分提供灵活的，对映体控制的策略而得到有效实现。讨论了非对称烯丙基化方法中立体控制的进展。努力的成果是使用Terashima氢化物试剂进行还原的新颖结果。[结构：见文字]

  DOI：

  10.1021/ol036071v
• 作为产物：
  描述：

  (2S,6R)-2-[1,3]dithian-2-ylmethyl-6-[2-(4-methoxybenzyloxy)ethyl]-4-methylenetetrahydropyran 在 水 、 calcium carbonate 、 碘甲烷 作用下， 以 乙腈 为溶剂， 以96%的产率得到((2S,6R)-6-[2-(4-methoxybenzyloxy)ethyl]-4-methylenetetrahydropyran-2-yl)-acetaldehyde
  参考文献：
  名称：

  Studies for the enantiocontrolled preparation of substituted tetrahydropyrans: applications for the synthesis of leucascandrolide A macrolactone

  摘要：

  Strategies for the stereocontrolled preparations of 2,6-cis- and 2,6-trans-substituted tetrahydropyrans have been devised. These studies have explored methodology for asymmetric induction in S-E' reactions using chiral 1,3,2-diazaborolidine controllers. Reactions with aldehydes at -78 degrees C yield nonracemic 1,5-diols for chemoselective internal backside displacements. This concept is developed as a flexible and reliable strategy in studies toward leucascandrolide A macrolactone 2 via the sequential applications of S-E' reactions leading to the C-1-C-9 aldehyde 14, and the bis-tetrahydropyran 59, respectively. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.05.020

文献信息

• Diastereoselectivity in asymmetric allylations: The role of vicinal chirality in the allyl nucleophile for S_E2′ reactions with aldehydes
  作者：David R Williams、Kevin G Meyer、Khalida Shamim、Samarjit Patnaik

  DOI：10.1139/v03-168

  日期：2004.2.1

  A series of nonracemic homoallylic alcohols have been prepared by asymmetric allylation using the (R,R)- and (S,S)-1,2-diamino-1,2-diphenylethane bis-sulfonamide controller ligands for in situ formation of chiral B-allyl-1,3,2-diazaborolidines. Diastereofacial selectivity is influenced by adjacent stereochemistry incorporated into the allyl moiety at C-2, in addition to the expected role of the chiral

  使用 (R,R)- 和 (S,S)-1,2-diamino-1,2-diphenylethane bis-sulfonamide 控制配体通过不对称烯丙基化制备了一系列非外消旋高烯丙醇，用于原位形成手性 B -烯丙基-1,3,2-二氮杂硼烷。除了手性助剂的预期作用外，非对映面选择性还受结合到 C-2 烯丙基部分的相邻立体化学的影响。醛反应物中的额外不对称性引入了三重立体分化。开发了一个模型来识别增强立体化学关系，并且示例已经确定了这些因素的相对重要性。该方法支持以高度收敛的方式构建复杂的高烯丙醇。 关键词：不对称烯丙基化，非对映选择性，1,4-立体控制，
• Formal Synthesis of Leucascandrolide A
  作者：David R. Williams、Scott V. Plummer、Samarjit Patnaik

  DOI：10.1002/anie.200351817

  日期：2003.8.25
• Studies for the enantiocontrolled preparation of substituted tetrahydropyrans: applications for the synthesis of leucascandrolide A macrolactone
  作者：David R. Williams、Scott V. Plummer、Samarjit Patnaik

  DOI：10.1016/j.tet.2011.05.020

  日期：2011.7

  Strategies for the stereocontrolled preparations of 2,6-cis- and 2,6-trans-substituted tetrahydropyrans have been devised. These studies have explored methodology for asymmetric induction in S-E' reactions using chiral 1,3,2-diazaborolidine controllers. Reactions with aldehydes at -78 degrees C yield nonracemic 1,5-diols for chemoselective internal backside displacements. This concept is developed as a flexible and reliable strategy in studies toward leucascandrolide A macrolactone 2 via the sequential applications of S-E' reactions leading to the C-1-C-9 aldehyde 14, and the bis-tetrahydropyran 59, respectively. (C) 2011 Elsevier Ltd. All rights reserved.
• Leucascandrolide A:  A Second Generation Formal Synthesis
  作者：David R. Williams、Samarjit Patnaik、Scott V. Plummer

  DOI：10.1021/ol036071v

  日期：2003.12.1

  A convergent, second generation formal synthesis of (+)-Leucascandrolide A (1) has been efficiently achieved by providing a flexible, enantiocontrolled strategy toward the bioactive macrolactone component. Advancements for stereocontrol in asymmetric allylation methodology are discussed. Efforts feature novel results for reductions using the Terashima hydride reagent. [structure: see text]

  （+）-Leucascandrolide A（1）的收敛的第二代正式合成已通过针对生物活性大内酯组分提供灵活的，对映体控制的策略而得到有效实现。讨论了非对称烯丙基化方法中立体控制的进展。努力的成果是使用Terashima氢化物试剂进行还原的新颖结果。[结构：见文字]