(2R,4R)-2,4-dimethylpentanolide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (2R,4R)-2,4-dimethylpentanolide
• 英文别名: (3R,5R)-3,5-dimethyloxan-2-one
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: BNTVLKCRDTXUOL-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,4R)-2,4-dimethylpentanolide 在 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 (2S,4S)-2,4-dimethylhept-5-yn-1-ol
  参考文献：
  名称：

  一种制备非末端炔烃的新方法：在Tulearin A和C的总合成中的应用

  摘要：

  已知内酯会以Wittig型方式与CCl 4和PPh 3原位生成的试剂反应，生成宝石二氯烯烃衍生物。现已证明此类化合物在用有机锂试剂RLi处理后会发生还原烷基化反应，从而提供在其末端带有R取代基的乙炔衍生物（R = Me，n-，仲-，叔烷基，甲硅烷基）；该反应可以用Cu（acac）2或Fe（acac）3催化/ 1,2-二氨基苯 从容易获得的内酯前体以这种方式制备的两种炔醇衍生物，是细胞毒性海洋大环内酯类鹅膏蛋白A（1）和C（2）的总合成的关键组成部分。这些易碎目标的组装取决于闭环炔烃复分解（RCAM），然后通过反式氢化硅烷化/原去甲硅烷基化对所得的环炔烃进行正式的反式还原。

  DOI：

  10.1002/chem.201404873
• 作为产物：
  描述：

  顺式-3,5-二甲基二氢-2H-吡喃-2,6(3H)-二酮 在 锂硼氢 作用下， 生成 (2R,4R)-2,4-dimethylpentanolide
  参考文献：
  名称：

  使用手性联萘基二胺衍生物不对称合成2,4-二甲基戊内酯和甲戊内酯

  摘要：

  轴向不对称的联萘二胺衍生物是由环状酸酐（3）和（4）的不对称开环在水解时闭合而形成的，得到具有74％ee的（-）-反式-2,4-二甲基戊内酯

  DOI：

  10.1039/c39840000779

文献信息

• Intramolecular Stereoselective Protonation of Aldehyde-Derived Enolates
  作者：Anastasie Kena Diba、Claudia Noll、Michael Richter、Marc Timo Gieseler、Markus Kalesse

  DOI：10.1002/anie.201004619

  日期：2010.11.2

  Picking sides: Asymmetric protonation of the titled compounds poses a most significant challenge and has been addressed by taking advantage of internal protonation and subsequent hemiacetal formation to avoid epimerization (see scheme). The substrates employed in these transformations can be easily accessed through a sequence of vinylogous aldol reactions with subsequent conjugate reductions.

  采摘方：标题化合物的不对称质子化构成了最重大的挑战，已通过利用内部质子化和随后的半缩醛形成来避免差向异构化（请参见方案）来解决。这些转化中使用的底物可以通过一系列的乙烯醇醛醇缩醛反应以及随后的共轭物还原而容易地获得。
• Remote Control of Regio- and Diastereoselectivity in the Hydroformylation of Bishomoallylic Alcohols with Catalytic Amounts of a Reversibly Bound Directing Group
  作者：Christian U. Grünanger、Bernhard Breit

  DOI：10.1002/anie.200905949

  日期：2010.1.25

  Remote and reversible! Phosphinites serve as reversibly bound directing groups for the remote control of the regio‐ and diastereoselective hydroformylation of bishomoallylic alcohols (see scheme; r.r: regioisomer ratio). The distance between the double bond and the functional hydroxy group to which the directing group is reversibly bound is the longest ever reported.

  远程且可逆！次膦酸酯是可逆结合的导向基团，用于远程控制双烯丙基烯丙醇的区域和非对映选择性加氢甲酰化（请参阅方案； rr：区域异构体比率）。双键与可逆结合的方向性羟基基团之间的距离是有史以来最长的。
• Synthesis of Microcolin B, a Potent New Immunosuppressant Using an Efficient Mixed Imide Formation Reaction
  作者：Merritt B. Andrus、Wenke Li、Robert F. Keyes

  DOI：10.1021/jo970387x

  日期：1997.8.1

  Microcolin B, a potent new immunosuppressant isolated from blue-green alga Lyngbya majuscula off the Venezuelan coast, has been made using a methyl-directed asymmetric hydrogenation reaction with rhodium on alumina catalyst on lactone 4 for the synthesis of the key (R,R)-2,4-dimethyloctanoic acid fragment 1. A new, direct mixed imide formation reaction was also developed for the production of the unusual prolylpyrrolen-2-one 2 portion of microcolin. The pentafluorophenyl ester of CBZ-proline 5 was reacted with the lithium imidate of lactam 6, providing the mixed imide in 80% yield. Coupling of acid 1 with the N-terminus of the tripeptide, followed by coupling with pyrrolylproline 2, gave microcolin B. The new mixed-imide forming reaction was also applied to a formal total synthesis of microcolin A. The pentafluorophenyl ester of TBS-protected cis-hydroxyproline was coupled with lactam 6, and the resultant imide was converted to the key pyrrolylproline made previously far microcolin A.
• The First Stereoselective Palladium-Catalyzed Cyclocarbonylation of β,γ-Substituted Allylic Alcohols
  作者：Melanie Brunner、Howard Alper

  DOI：10.1021/jo9702709

  日期：1997.10.1

  beta,gamma-Substituted allylic alcohols react with CO in the presence of catalytic quantities of palladium acetate and 1,4-bis(diphenylphosphino)butane affording alpha,beta-substituted-gamma-butyrolactones in 42-85% isolated yields. The complete stereoselectivity observed in some cases is a significant feature of the lactonization reaction, with (E)-allylic alcohols affording trans-disubstituted lactones. Depending on the structure of the allylic alcohol used in the cyclocarbonylation reaction, the formation of the corresponding alkene or the beta,gamma-unsaturated carboxylic acid was observed as a side or the principal reaction.
• Kawakami, Yukio; Hiratake, Jun; Yamamoto, Yukio, Agricultural and Biological Chemistry, 1986, vol. 50, # 3, p. 693 - 698
  作者：Kawakami, Yukio、Hiratake, Jun、Yamamoto, Yukio、Oda, Jun'ichi

  DOI：——

  日期：——