(2R,trans)-3-hexyloxiranemethyl tosylate | 147048-01-9

• 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: (2R,trans)-3-hexyloxiranemethyl tosylate
• 英文别名: [(2R,3R)-3-hexyloxiran-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 147048-01-9
• 化学式: C₁₆H₂₄O₄S
• 分子量: 312.43
• InChiKey: STJDVQFRQSPGTM-HZPDHXFCSA-N

物化性质

• 沸点：
  434.4±18.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,trans)-3-hexyloxiranemethyl tosylate 在 sodium hydroxide 、 碲化氢 、 sodium formaldehyde sulfoxylate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以97%的产率得到(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：

  ((2R,3R)-3-hexyloxiran-2-yl)methanol 、 对甲苯磺酰氯 在 三乙胺 作用下， 以 氯仿 为溶剂， 以85%的产率得到(2R,trans)-3-hexyloxiranemethyl tosylate
  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

• Chemoselective reduction of 2,3-epoxy tosylates with DIBAL-H as a general route to enantiomerically-enriched 1-tosyloxy-2-alkanols
  作者：J. Michael Chong、James Johannsen

  DOI：10.1016/0040-4039(94)85359-2

  日期：1994.9

  2,3-Epoxy tosylates may be reduced with DIBAL-H in CH2Cl2 or ether at −40 °C to 1-tosyloxy-2-alkanols in high (94–98%) yields.

  用DIBAL-H的CH 2 Cl 2溶液或乙醚在-40°C下可将2,3-环氧甲苯磺酸酯还原为1-甲苯磺酰氧基-2-链烷醇，产率高（94-98％）。
• Chong J. Michael, Johannsen James, Tetrahedron Lett, 35 (1994) N 39, S 7197-7200
  作者：Chong J. Michael, Johannsen James

  DOI：——

  日期：——
• A tellurium transposition route to allylic alcohols: overcoming some limitations of the Sharpless-Katsuki asymmetric epoxidation
  作者：Donald C. Dittmer、Robert P. Discordia、Yanzhi Zhang、Christopher K. Murphy、Archana Kumar、Aurora S. Pepito、Yuesheng Wang

  DOI：10.1021/jo00055a029

  日期：1993.1

  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.
• Stereoconvergent synthesis of enantiopure (-)-trans-lauthisan. Building kit for medium ring oxacycle construction and contrathermodynamic epimerization at allylic carbon C(8) via “invisible”, E-configurated medium ring olefin
  作者：H.M.R Hoffmann、Arndt Brandes

  DOI：10.1016/0040-4020(94)00960-3

  日期：1995.1

  Starting once more from simple, acyclic, functionalized α,α′-chiral, disecondary ethers we have prepared enantiomerically pure (-)-trans-lauthisan (which is thermodynamically less stable than its cis-epimer). During a Pd(0) catalyzed cyclization a strained E-configurated, 8-membered allylic ether (as an η2 palladium complex) is believed to be a reactive intermediate, in which the oxygen of the allylic

  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。