Toluene-4-sulfonic acid <3-methyl-3-(4-methylpent-3-enyl)oxiran-2-yl>methyl ester | 121401-06-7

• 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: Toluene-4-sulfonic acid <3-methyl-3-(4-methylpent-3-enyl)oxiran-2-yl>methyl ester
• 英文别名: 1-tosyl-2,3-epoxygeraniol；[(2S,3S)-3-methyl-3-(4-methylpent-3-enyl)oxiran-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 121401-06-7
• 化学式: C₁₇H₂₄O₄S
• 分子量: 324.441
• InChiKey: DPTURXDQMJHFIW-IRXDYDNUSA-N

物化性质

• 沸点：
  435.4±18.0 °C(Predicted)
• 密度：
  1.120±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  Toluene-4-sulfonic acid <3-methyl-3-(4-methylpent-3-enyl)oxiran-2-yl>methyl ester 在 sodium hydroxide 、 碲化氢 、 rongalite 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 生成 (S)-芳樟醇
  参考文献：
  名称：

  A catlaytic tellurium process for the transposition of allylic hydroxyl groups and carbon-carbon double bonds

  摘要：

  As little as 0.1 molar equivalent of elemental tellurium in combination with excess (up to 3 molar equivalents) reducing agent (HOCH2SO2Na.2H2O, NaBH4, or LiEt(3)BH) effects the telluride-ion mediated transposition of allylic hydroxyl groups and carbon-carbon double bonds that proceeds via the epoxy tosylate. The workup is much more convenient than when a molar equivalent of tellurium is used.

  DOI：

  10.1016/s0040-4039(00)77252-2
• 作为产物：
  描述：

  香叶醇 在 吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二异丙酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 26.0h， 生成 Toluene-4-sulfonic acid <3-methyl-3-(4-methylpent-3-enyl)oxiran-2-yl>methyl ester
  参考文献：
  名称：

  Total synthesis of the meso-triterpene polyether teurilene

  摘要：

  The first total synthesis of the triterpene ether teurilene (1) has been accomplished utilizing two vanadium(V)-catalyzed oxidation-cyclization reactions with different stereoselectivities. The synthesis involved stereoselective and step-by-step construction of 2,5-cis- and 2,5-trans-tetrahydrofuran rings, vanadium(V)-catalyzed oxidation of 4-substituted 4-en-1-ol 40 and subsequent cyclization of the resulting anti-epoxy alcohol 41, and a similar oxidation-cyclization of 5-substituted 4-en-1-ol 49 by way of syn-epoxy alcohol 50. This was followed by construction of a third tetrahydrofuran ring by more conventional means. An improved synthesis of 1, which featured direct formation of bis(tetrahydrofuran) 51 from squalene derivative 66 by simultaneous double oxidation-cyclization, was also accomplished.

  DOI：

  10.1021/jo00007a013

文献信息

• Synthesis of (E)-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid and the corresponding amide (“acacialactam”) in optically active form
  作者：Miguel Carda、Juan Murga、Florenci González、J Alberto Marco

  DOI：10.1016/0040-4020(95)00025-4

  日期：1995.2

  The total synthesis of the title compounds in optically active form from geraniol as the starting material is described. The physical and spectral properties of the synthetic amide are identical with those of the natural compound acacialactam, this fact confirming that the structure proposed for the latter compound is not correct. The configuration of the single stereogenic carbon atom in the natural

  描述了由香叶醇作为起始原料以光学活性形式的标题化合物的全合成。合成酰胺的物理和光谱性质与天然化合物阿拉伯胶内酰胺的相同，这一事实证实了对于后一种化合物提出的结构是不正确的。在天然酰胺单立体碳原子的构型被示出为小号。
• Simple one-pot transformations of toluene-p-sulfonates of 2,3-epoxy alcohols into allylic alcohols
  作者：Nobutaka Fujii、Hiromu Habashita、Masako Akaji、Kazuo Nakai、Toshiro Ibuka、Masahiro Fujiwara、Hirokazu Tamamura、Yoshinori Yamamoto

  DOI：10.1039/p19960000865

  日期：——

  A simple synthetic method for the preparation of scalemic allylic alcohols from toluene-p-sulfonates of scalemic 2,3-epoxy alcohols is reported. Satisfactory yields are obtained by treatment of toluene-p-sulfonates of 2,3-epoxy alcohols with potassium iodide followed by triphenylphosphine and iodine in a one-pot synthesis.

  报道了一种简单的合成方法，该方法由规模化的2,3-环氧醇的甲苯-对-磺酸盐制备规模化的烯丙醇。通过一锅合成法，先用碘化钾，然后用三苯基膦和碘处理碘化2,3-环氧醇的甲苯对磺酸酯，可获得令人满意的收率。
• Base-Mediated, Chemo- and Regioselective (4+2) Annulation of Indole-2-carboxamides with 2,3-Epoxy Tosylates toward 1,2-Fused Indoles
  作者：Arup Jyoti Das、Sajal Kumar Das

  DOI：10.1021/acs.joc.3c00813

  日期：2023.7.7

  indole-2-carboxamides with 2,3-epoxy tosylates has been explored. The protocol delivers 3-substituted pyrazino[1,2-a]indol-1-ones in high yields in diastereoselective fashion, and neither 4-substituted pyrazino[1,2-a]indol-1-ones nor tetrahydro-1H-[1,4]diazepino[1,2-a]indol-1-ones are generated, irrespective of whether the distal epoxide C3 substituent is alkyl or aryl, or the epoxide is cis- or trans-configured

  已经探索了吲哚-2-甲酰胺与 2,3-环氧甲苯磺酸盐的碱介导[4+2]环化。该方案以非对映选择性方式以高产率提供 3-取代的吡嗪[1,2- a ]吲哚-1-酮，并且既不产生 4-取代的吡嗪[1,2- a ]吲哚-1-酮，也不产生四氢-1 H-无论远端环氧化物C3取代基是烷基还是芳基，或者环氧化物是顺式还是反式，都会生成[1,4]二氮杂[1,2- a ]吲哚-1-酮-配置。该反应通过用 2,3-环氧甲苯磺酸酯对吲哚支架进行 N-烷基化，同时进行 6-外选择性环氧化物开环反应，在一锅中进行。值得注意的是，该过程对于两种起始材料都具有化学和区域选择性。据我们所知，该过程代表了吲哚基二杂核亲核试剂与环氧化物基介电试剂一锅成环的第一个成功例子。
• 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.
• De Novo Synthesis of (+)-Isofregenedol
  作者：Maxime Riou、Louis Barriault

  DOI：10.1021/jo801365z

  日期：2008.9.19

  An efficient enantioselective synthesis of (+)-isofregenedol was achieved in 13 steps from commercially available cyclohexene oxide without the use of protecting groups. The tetrahydronaphthalenic core of isofregenedol was obtained via a gold(I)-catalyzed benzannulation recently developed in our laboratory.