((2R,3R)-3-hexyloxiran-2-yl)methanol | 107796-93-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: ((2R,3R)-3-hexyloxiran-2-yl)methanol
• 英文别名: [(2R,3R)-3-hexyloxiran-2-yl]methanol；(2R,trans)-3-hexyloxiranmethanol；(2R,3R)-(+)-2,3-Epoxy-1-nonanol；(2R,3R)-(+)-epoxy-2-nonen-1-ol；(2S,3R)-2,3-epoxy-1-nonanol
• CAS: 107796-93-0
• 化学式: C₉H₁₈O₂
• 分子量: 158.241
• InChiKey: UDSPJJHSJCWGQS-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ((2R,3R)-3-hexyloxiran-2-yl)methanol 在 4-二甲氨基吡啶 、 sodium hydroxide 、 碲化氢 、 sodium formaldehyde sulfoxylate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (R)-non-1-en-3-ol
  参考文献：
  名称：

  A tellurium transposition route to allylic alcohols: overcoming some limitations of the Sharpless-Katsuki asymmetric epoxidation

  摘要：

  Good yields of enantiomeric allylic alcohols can be obtained in high enantiomeric excess (ee) by combining the Sharpless-Katsuki asymmetric epoxidation process (SAE) with tellurium chemistry. The advantages of the tellurium process are as follows: (1) the 50% yield limitation on the allylic alcohol in the Sharpless kinetic resolution (SKR) can be overcome; (2) allylic tertiary alcohols which are unsatisfactory substrates in the SKR can be obtained in high optical purity; (3) optically active secondary allylic alcohols with tertiary alkyl substituents (e.g. tert-butyl) at C-1 can be obtained in high ee; (4) optically active sterically congested cis secondary alcohols can be obtained in high ee; and (5) the nuisance of the slow SAE of some vinyl carbinols can be avoided. The key step in the reaction sequence is either a stereospecific 1,3-trans position of double bond and alcohol functionalities or an inversion of the alcohol configuration with concomitant deoxygenation of the epoxide function in epoxy alcohols. Trans secondary allylic alcohols can be converted to cis secondary allylic alcohols by way of erythro epoxy alcohols (glycidols); threo glycidyl derivatives are converted to trans secondary allylic alcohols. These transformations are accomplished by the action of telluride ion, generated in situ from the element, on a glycidyl sulfonate ester. Reduction of elemental Te is conveniently done with rongalite (HOCH2SO2Na) in an aqueous medium. This method is satisfactory when Te2- is required to attack a primary carbon site of a glycidyl sulfonate. In cases where Te2- is required to attack a secondary carbon site, reduction of the tellurium must be done with NaBH4 or LiEt3BH. Elemental tellurium is precipitated during the course of the reactions and can be recovered and reused.

  DOI：

  10.1021/jo00055a029
• 作为产物：
  描述：

  反-2-壬烯-1-醇 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 molecular sieve 、 (-)-diethyl tartrate 作用下， 以 二氯甲烷 为溶剂， 以65%的产率得到((2R,3R)-3-hexyloxiran-2-yl)methanol
  参考文献：
  名称：

  对映体（-）-反式-lauthisan的立体收敛合成。用于中环氧杂二环结构和通过“不可见”，E构型的中环烯烃在烯丙基碳C（8）上进行反热力学差向异构化的构建套件

  摘要：

  从简单的，无环的，官能化的α，α'-手性二仲醚开始，我们制备了对映体纯的（-）-反式-lauthisan（在热力学上比其顺式-epimer不稳定）。在钯（0）催化的环化反应的应变E-可配置，8-元烯丙基醚（作为η 2钯复合物）被认为是反应性的中间体，其中所述烯丙基醚届氧离去基团的状态和contrathermodynamically重新闭合并立体收敛于分离的α，α'-反式构型的中环醚。9元环（参见前面的论文）建议由类似的序列形成。

  DOI：

  10.1016/0040-4020(94)00960-3

文献信息

• Cyclic Sulfur Ylides Derived from Gleason-Type Chiral Auxiliaries for the Asymmetric Synthesis of Epoxy Amides
  作者：Francisco Sarabia、Carlos Vivar-García、Miguel García-Castro、Jorge Martín-Ortiz

  DOI：10.1021/jo1025964

  日期：2011.5.6

  Gleason-type chiral auxiliaries were used for the synthesis of a novel class of sulfonium salts, obtained via methylation of the sulfide with Meerwein's salt. The salts were reacted with aldehydes under basic conditions to provide epoxy amides, which were reduced to their corresponding epoxy alcohols in excellent enantiomeric excesses. Interestingly, it was feasible to synthesize both enantiomeric

  格里森型手性助剂用于合成一类新型的salts盐，该via盐是通过用Meerwein盐将硫化物甲基化而获得的。该盐在碱性条件下与醛反应，得到环氧酰胺，将其以优异的对映体过量还原为相应的环氧醇。有趣的是，它是合成两个对映异构体的环氧醇，这取决于所述锍盐的可行的，从制备升α-氨基酸（6和9从升-缬氨酸或15和16从升-丝氨酸）中的溶液使用。
• Asymmetric Epoxidation of α,β-Unsaturated Aldehydes in Aqueous Media Catalyzed by Resin-Supported Peptide- Containing Unnatural Amino Acids
  作者：Kengo Akagawa、Kazuaki Kudo

  DOI：10.1002/adsc.201000805

  日期：2011.4.18

  The enantio‐ and diastereoselective epoxidation of α,β‐unsaturated aldehydes in aqueous media was realized using a resin‐supported peptide catalyst. Introducing the hydrophobic and bulky unnatural amino acid 3‐(1‐pyrenyl)alanine into the peptide sequence was effective for enhancing the reaction rate and enantioselectivity.

  使用树脂负载的肽催化剂可实现水性介质中α，β-不饱和醛的对映体和非对映体选择性环氧化。在肽序列中引入疏水和庞大的非天然氨基酸3-（1-吡啶基）丙氨酸可有效提高反应速度和对映选择性。
• A convenient synthesis of aziridine-2-carboxylic esters
  作者：Johan Legters、Lambertus Thijs、Binne Zwanenburg

  DOI：10.1002/recl.19921110101

  日期：——

  Optically active oxirane-2-carboxylic esters, prepared from allylic alcohols employing the Sharpless epoxidation, were treated with sodium azide. The azido alcohols obtained were subsequently converted into aziridine-2-carboxylic esters by reaction with triphenylphosphine, in good yields and with high optical purity. Various racemic oxirane-2-carboxylic esters were subjected to the same sequence of

  用叠氮化钠处理由使用Sharpless环氧化的烯丙基醇制备的旋光环氧乙烷-2-羧酸酯。随后通过与三苯基膦反应以高收率和高光学纯度将获得的叠氮基醇转化为氮丙啶-2-羧酸酯。使各种外消旋环氧乙烷-2-羧酸酯进行相同的反应顺序。
• Use of asymmetric propargyl dicobalt hexacarbonyl complexes in organic synthesis: Access to enantiomerically pure α-hydroxy acid derivatives
  作者：Juan M. Betancort、Carmen Ma Rodríguez、Víctor S. Martín

  DOI：10.1016/s0040-4039(98)02170-4

  日期：1998.12

  The trapping under different conditions of the carbocation generated by acid treatment of chiral Co2(CO)6-complexed propargylic secondary alcohols permitted access to either diastereoisomer at the propargylic center. Further chemical manipulations provided either enantiomer of enantiomerically pure 1,2-difunctionalized molecules such as 1,2-diols, α-hydroxy-aldehydes or α-hydroxy-acids.

  通过酸处理手性Co 2（CO）6络合的炔丙基仲醇生成的碳正离子在不同条件下的捕集允许在炔丙基中心进入任一非对映异构体。进一步的化学操作提供了对映体纯的1,2-双官能化分子的对映体，例如1,2-二醇，α-羟基醛或α-羟基酸。
• Solid Phase Synthesis of Globomycin and SF-1902 A₅
  作者：Francisco Sarabia、Samy Chammaa、Cristina García-Ruiz

  DOI：10.1021/jo1025145

  日期：2011.4.1

  peptidic fragment and a new asymmetric methodology of epoxidation for the preparation of the lipidic chain. The linkage between both fragments was successfully achieved in solid phase to complete the syntheses via a macrolactonization reaction executed prior to the cleavage of the acyclic precursors from the solid support. These syntheses provide access to the rapid generation of a library of analogues

  报道了天然脂环二肽类抗生素球霉素和SF-1902 A 5的合成，利用固相技术构建了肽片段，并采用了一种新的不对称环氧化方法来制备脂​​质链。两个片段之间的键合在固相中成功完成，通过在从固体载体上裂解无环前体之前进行的大环内酯化反应完成了合成。这些合成物通过修饰氨基酸残基和脂质链提供了快速生成类似物文库的途径，从而基于对酶信号肽酶II的抑制，促进了具有有趣作用机制的新抗生素的鉴定。