(2R,3S,4S)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol | 181139-28-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4S)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol
• 英文别名: (2R,3S,4S)-2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol；(1S,2S)-1-[(3R)-1,4-dioxaspiro[4.5]decan-3-yl]-2-methylbut-3-en-1-ol
• CAS: 181139-28-6
• 化学式: C₁₃H₂₂O₃
• 分子量: 226.316
• InChiKey: BRKSCMKFXDKAJL-TUAOUCFPSA-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

• 作为反应物：
  描述：

  (2R,3S,4S)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol 在 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 10.5h， 生成 (2R,3S,4S)-4-methyl-3-(phenylmethoxy)-5-hexene-1,2-diol
  参考文献：
  名称：

  (3R, 4S)-4-Methyl-3-hexanol 和 (S)-4-Methyl-3-己酮，蚂蚁的信息素的方便合成

  摘要：

  使用由 D-甘露醇制备的化合物 2 作为手性前体，合成了对映体纯信息素 I 和 II，它们都带有手性甲基支链和 α-氧化碳中心。

  DOI：

  10.3390/50801051
• 作为产物：
  描述：

  1-溴-2-丁烯 、 (S)-cyclohexylidene glyceraldehyde 在 tin(II) chloride dihdyrate 、 氢化铝 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 (2R,3R,4R)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol 、 (2R,3S,4R)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol 、 (2R,3S,4S)-1,2-cyclohexylidenedioxy-4-methylhex-5-en-3-ol
  参考文献：
  名称：

  A practical procedure of low valent tin mediated Barbier allylation of aldehydes in wet solvent

  摘要：

  Use of aluminium as the reducing metal in spontaneous bimetal redox reaction has been elegantly exploited for allylation/crotylation of aldehydes in wet solvent. Here, low valent tin was prepared in situ by reduction of SnCl2 center dot 2H(2)O with aluminium in THF/water. The resulting low valent tin acted as an efficient mediator for allylation and crotylation of aldehydes (3a-q) producing the corresponding homoallylic alcohols. The efficacy of this procedure was due to its operational simplicity, practical viability, inexpensiveness, good yields of the products and short reaction time. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.09.096

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。