cis-2-cyclohexenyl-1,4-diacetate | 78776-45-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: cis-2-cyclohexenyl-1,4-diacetate
• 英文别名: cis-1,4-diacetoxy-2-cyclohexene；cis-1,4-diacetoxycyclohexene；[(1S,4R)-4-acetyloxycyclohex-2-en-1-yl] acetate
• CAS: 78776-45-1
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: VDGAZJWPUNUMLR-AOOOYVTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cis-2-cyclohexenyl-1,4-diacetate 在 盐酸 、 sodium chlorate 、 四氧化锇 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 54.0h， 生成 cyclohexanetetrol-(1r,2t,3t,4c)
  参考文献：
  名称：

  六种 1, 2, 3, 4-环己四醇中四种的简便立体选择性合成：提高环醇对糖类分子识别的可及性

  摘要：

  摘要 (1,2,3/4)-, (1,2/3,4)-, (1,4/2,3)- 和 (1,2,4/3)- 的新立体选择性合成描述了环己四醇（分别为 1、2、3 和 4）。已知的顺式和反式 1,4-环己-2-烯二醇 9 和 10 用作起始材料。二醇 9 和 10 可以与 OsO4 反应，分别直接形成 3 和 1。二醇 9 和 10 用 MCPBA 环氧化，在酸催化环氧化物开环后产生 4 和 2。

  DOI：

  10.1080/00397919408010592
• 作为产物：
  描述：

  (1R,1S)-2,3-dioxabicyclo[2.2.2]oct-5-ene 在 硫脲 作用下， 以 吡啶 、 甲醇 为溶剂， 反应 8.0h， 生成 cis-2-cyclohexenyl-1,4-diacetate
  参考文献：
  名称：

  Synthesis of branched carbasugars via photooxygenation and manganese(III) acetate free radical cyclization

  摘要：

  Transformation of cyclohexa-1,3- and 1,4-dienes to carbasugars is described. Photooxygenation of dienes gave bicyclic endoperoxides, which were reduced with thiourea to the corresponding 1,4-dials with cis-configuration. Lactonization of the remaining double bond by oxidative addition of acetic acid to the double bond in the presence of Mn(OAc)(3) followed by lactone ring-opening reaction gave the target branched carbasugars. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.05.069

文献信息

• Analogues of the 2-carboxyl-6-hydroxyoctahydroindole (CHOI) unit from diverging Pd-catalyzed allylations: Selectivity as a function of the double bond position
  作者：Zhongyi Mao、Elisabetta Martini、Guillaume Prestat、Julie Oble、Pei-Qiang Huang、Giovanni Poli

  DOI：10.1016/j.tetlet.2017.09.046

  日期：2017.11

  bearing an unsaturation in different positions. Sequential homologation, and epoxidation or syn-dihydroxylation steps were investigated to access analogues of the bicyclic 2-carboxyl-6-hydroxyoctahydroindole motif of aeruginosins, a family of peptides displaying serine protease inhibitor activity.

  钯催化的环状双烯丙基底物的烯丙基化，以两个单独的步骤或以假多米诺方式进行，可以生成在不同位置带有不饱和键的2-羧基-六氢吲哚。为了获得铜绿素酶的双环2-羧基-6-羟基八氢吲哚基序的序列类似物，环氧化或顺-二羟基化步骤进行了研究，这是一个显示丝氨酸蛋白酶抑制剂活性的肽家族。
• Pyrrolizidine Alkaloids by Intramolecular Palladium-Catalysed Allylic Alkylation: Synthesis of (±)-Isoretronecanol
  作者：Sébastien Lemaire、Giuliano Giambastiani、Guillaume Prestat、Giovanni Poli

  DOI：10.1002/ejoc.200400135

  日期：2004.7

  An efficient and stereoconvergent approach to 3-substituted hexahydroindol-2-one derivatives by palladium-catalysed intramolecular allylic alkylation has been developed. Subsequently, the straightforward conversion of the hexahydroindol-2-one 7d into the alkaloid (±)-isoretronecanol has been performed. The synthesis entails 11 steps starting from 1,3-cyclohexadiene, affording the final target in a

  已开发出一种通过钯催化的分子内烯丙基烷基化来制备 3-取代的六氢吲哚-2-one 衍生物的有效立体收敛方法。随后，六氢吲哚-2-one 7d 直接转化为生物碱 (±)-isoretronecanol。该合成需要从 1,3-环己二烯开始的 11 个步骤，以 29% 的总产率提供最终目标。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Palladium-catalysed enantiodivergent synthesis of cis- and trans-4-aminocyclohex-2-enols
  作者：Roberto G. P. Gatti、Anna L. E. Larsson、Jan-E. Bäckvall

  DOI：10.1039/a600779a

  日期：——

  Enantiomerically pure cis- and trans-4-aminocyclohex-2-enols are prepared from cyclohexa-1,3-diene via (-)-cis-(1R,4S )-4-acetoxycyclohex-2-enol (-)-2a using palladium(0) chemistry. Benzylamine and diethylamine are tested in the Pd0-catalysed allylic amination reactions. Since acetate is too slow as a leaving group and gave considerable amounts of side products, a number of leaving groups have been investigated. Of these phosphinate and 2,4-dichlorobenzoate are excellent leaving groups and result in efficient and highly stereoselective reactions; chloride as allylic leaving group also gives good results. By variation of the leaving group and proper choice of the protecting group it is possible to synthesise all four stereoisomers of 4-aminocyclohex-2-enol in good yield and high enantiomeric excess.

  通过钯(0)化学方法，从环己二烯-1,3出发，经（-）-顺-（1R,4S）-4-乙酰氧基环己烯-2-醇（-）-2a，制备了手性纯的顺式和反式-4-氨基环己烯-2-醇。在钯0催化的烯丙基胺化反应中，测试了苄胺和二乙胺。由于乙酸酯作为离去基团过于缓慢，并产生了大量副产物，因此研究了多种离去基团。其中，膦酸酯和2,4-二氯苯甲酸酯是优良的离去基团，能实现高效且高度立体选择性的反应；氯作为烯丙基离去基团也取得了良好结果。通过变换离去基团并适当选择保护基团，可以高产率和高对映体过量地合成4-氨基环己烯-2-醇的全部四种立体异构体。
• Palladium-Catalyzed Approach to Substituted Dihydrofurans, Cyclopenta[<i>b</i>]furans and Tetrahydrobenzofurans
  作者：Shinji Tanimori、Mitsunori Kirihata

  DOI：10.1055/s-2006-950376

  日期：2007.1

  The reaction of a symmetrical allylic dicarbonate or diacetate with a variety of β-keto esters in the presence of a palladium catalyst gave 2-substituted 5-vinyl-4,5-dihydrofuran-3-carboxylates, 4,6a-dihydro-3aH-cyclopenta[b]furan-3-carboxylates, and 3a,4,5,7a-tetrahydrobenzofuran-3-carboxylates in moderate to good yields.

  在钯催化剂存在下，对称烯丙基二碳酸酯或二乙酸酯与多种β-酮酯反应，以中等至良好的收率得到了2-取代的5-乙烯基-4,5-二氢呋喃-3-羧酸酯、4,6a-二氢-3aH-环戊[b]呋喃-3-羧酸酯以及3a,4,5,7a-四氢苯并呋喃-3-羧酸酯。
• Expanding the Scope of Biomass-Derived Chemicals through Tandem Reactions Based on Oxorhenium-Catalyzed Deoxydehydration
  作者：Mika Shiramizu、F. Dean Toste

  DOI：10.1002/anie.201307564

  日期：2013.12.2

  New modes of DODH: Oxorhenium compounds act as deoxydehydration(DODH)/acid dual‐purpose catalysts to transform biomass‐derived diol substrates into a variety of commodity chemical precursors. The power of this approach is highlighted by a tandem [1,3]‐OH shift/DODH of 2‐ene‐1,4‐diols and 2,4‐diene‐1,6‐diols, and by a DODH/esterification sequence of sugar acids to unsaturated esters for the production

  DODH的新模式：氧化hen化合物充当脱氧脱水（DODH）/酸两用催化剂，将生物质衍生的二醇底物转化为多种商品化学前体。通过2-烯-1,4-二醇和2,4-二烯-1,6-二醇的串联[1,3] -OH移位/ DODH以及DODH /酯化序列突出了这种方法的优势糖酸到不饱和酯的合成，用于生产聚合物和增塑剂。