(2R,3R,4R)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4R)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol
• 英文别名: (2R,3R,4R)-2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol；(1R,2R)-2-methyl-1-((R)-1,4-dioxaspiro[4.5]decan-2-yl)but-3-en-1-ol；(1R,2R)-1-[(3R)-1,4-dioxaspiro[4.5]decan-3-yl]-2-methylbut-3-en-1-ol
• 化学式: C₁₃H₂₂O₃
• 分子量: 226.316
• InChiKey: BRKSCMKFXDKAJL-IJLUTSLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (2R,4R)-1,2-cyclohexylidenedioxy-4-methyl-5-hexen-3-one 在 potassium tri-sec-butyl-borohydride 作用下， 以 四氢呋喃 为溶剂， 生成 (2R,3R,4R)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol
  参考文献：
  名称：

  Metal-dependent modulation of diastereoselectivity in the Barbier-type crotylation of (R)-cyclohexylideneglyceraldehyde

  摘要：

  The diastereoselectivity of the Barbier-type crotylation of (R)-cyclohexylideneglyceraldehyde could be tuned by changing the metal atom and solvent. The Ga-mediated reaction in [bmim][Br] produced the best diastereoselectivity, furnishing the all-anti product in good yield. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.08.013

文献信息

• [bmim][Br] as an Inexpensive and Efficient Medium for the Barbier-Type Allylation Reaction Using a Catalytic Amount of Indium: Mechanistic Studies
  作者：Papiya Dey、Mrunesh Koli、Dibakar Goswami、Anubha Sharma、Subrata Chattopadhyay

  DOI：10.1002/ejoc.201800043

  日期：2018.3.22

  The Barbier‐type allylation of aldehydes and ketones can be carried out with both unsubstituted and γ‐substituted allyl bromides using only a catalytic amount (0.1 equiv.) of In metal in [bmim][Br].

  醛和酮的Barbier型烯丙基化反应可以在[bmim] [Br]中仅使用催化量（0.1当量）的In金属与未取代和γ-取代的烯丙基溴进行。
• syn-Selective crotylation of aldehydes using bismuth-crotyl bromide-(1-butyl-3-methylimidazolium bromide) combination: some synthetic applications
  作者：Dibakar Goswami、Mrunesh R. Koli、Sucheta Chatterjee、Subrata Chattopadhyay、Anubha Sharma

  DOI：10.1039/c7ob00626h

  日期：——

  The Bi-[bmim][Br] combination has been found to offer high syn-selectivity in the crotylation of aldehydes with crotyl bromide using practically stoichiometric amounts of the reagents. The room temperature ionic liquid (RTIL), [bmim][Br], activated Bi metal in the presence of oxygen to produce crotylbismuthdibromide, which reacted with the aldehydes at room temperature. The major anti–syn diastereomeric

  所述双环[BMIM] [BR]组合已被发现提供高顺式-选择性使用几乎化学计量的量的试剂与巴豆基溴醛的crotylation。室温离子液体（RTIL）[bmim] [Br]在氧气存在下活化Bi金属，生成crotylbismuthdibromide，后者在室温下与醛反应。主要的抗-顺式从（的crotylation得到非对映体产物- [R）-cyclohexylideneglyceraldehyde被用于dictyostatin和的cryptophycin段，和（+）的合成-顺-aerangis内酯，使用标准合成方案。
• An Asymmetric Synthesis of (-)-Prelactone B
  作者：Subrata Chattopadhyay、Avinash Salaskar、Narayan Mayekar、Anubha Sharma、Sandip Nayak、Angshuman Chattopadhyaya

  DOI：10.1055/s-2005-916009

  日期：——

  An efficient synthesis of (-)-prelactone B has been developed using 1,2-cyclohexylidene glyceraldehyde as the chiral template. The key features of the synthesis were stereoselective crotylation of 1,2-cyclohexylidene glyceraldehyde and enantioselective reduction of a ketone, as well as operational simplicity and use of inexpensive reagents/chemicals.

  已经开发出一种高效合成(-)-prelactone B的方法，采用1,2-环己烯基甘油醛作为手性模板。该合成的关键特点是1,2-环己烯基甘油醛的立体选择性克罗提化和酮的对映选择性还原，以及操作简便和使用廉价试剂/化学品。
• A convenient asymmetric synthesis of the octalactin lactone
  作者：Anubha Sharma、Sunita Gamre、Siddharth Roy、Dibakar Goswami、Angshuman Chattopadhyay、Subrata Chattopadhyay

  DOI：10.1016/j.tetlet.2008.04.058

  日期：2008.6

  A facile asymmetric synthesis of the octalactin lactone was developed staring from (R)-cyclohexylideneglyceraldehyde (1). The key step of the synthesis is an In-mediated diastereoselective crotylation of 1 in water, which furnished the building blocks with the required stereochemistry under operationally simple conditions. Their conversion to the appropriate intermediates, invertive esterification

  从（R）-环己基亚甘油醛（1）开始发展了八actin内酯的简便不对称合成。合成的关键步骤是在水中进行1的In介导的非对映选择性crotylation ，可在操作简单的条件下为构建基块提供所需的立体化学。它们转化为合适的中间体，反相酯化反应和闭环复分解反应提供了目标化合物。
• Crotylation of (R)-2,3-O-cyclohexylideneglyceraldehyde: a simple synthesis of (+)-trans-oak lactone
  作者：Angshuman Chattopadhyay、Dibakar Goswami、Bhaskar Dhotare

  DOI：10.1016/j.tetlet.2010.05.070

  日期：2010.7

  a representative example of chiral β,γ-disubstituted-γ-butyrolactones. In this endeavor, crotylations of 1 in THF mediated with four low valent metals were studied. All these reactions took place efficiently producing 2 in good yields but with varied stereoselectivities. Each reaction produced the corresponding secondary alcohol adduct 2b and 2c predominantly with diastereoisomer 2a only in trace amounts

  （R）-2,3-环己基甘油醛（1）的丁酰化被用于反式-橡木内酯（I）的简单合成，反式-橡木内酯（I）是手性β，γ-二取代-γ-丁内酯的代表实例。在这一努力中，研究了由四种低价金属介导的THF中1的丁酰化。所有这些反应均有效地进行，以高产率产生2，但具有不同的立体选择性。每个反应主要仅以痕量产生相应的仲醇加合物2b和2c，主要与非对映异构体2a一起产生。在这四个反应中，只有Sn介导的加成反应产生2b作为主要产品。后来，2c通过氧化还原转化为2d。最后，仅需几个步骤，即可将2c转化为反式-橡木内酯I。按照此路线，2a，2b和2d将产生橡木内酯的其他立体异构体。