rac-(1R,5R,6S)-3-methoxycarbonyl-7-oxabicyclo[4.1.0]hept-2-en-5-ol

• 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: rac-(1R,5R,6S)-3-methoxycarbonyl-7-oxabicyclo[4.1.0]hept-2-en-5-ol
• 英文别名: methyl trans-3,4-epoxy-5-hydroxy-cyclohexene-1-carboxylate；methyl (1S,5S,6R)-5-hydroxy-7-oxabicyclo[4.1.0]hept-2-ene-3-carboxylate
• 化学式: C₈H₁₀O₄
• 分子量: 170.165
• InChiKey: LHPOIQVOXOVXFQ-LYFYHCNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  59.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  rac-(1R,5R,6S)-3-methoxycarbonyl-7-oxabicyclo[4.1.0]hept-2-en-5-ol 在 bis(acetylacetonate)oxovanadium 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 Pseudomonas stutzeri lipase (Meito TL) 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 67.0h， 生成 (1R,2S,4S,5R,7R)-7-(tert-butyldimethylsilanyloxymethyl)-3,8-dioxatricyclo[5.1.0.0^2,4]octan-5-ol
  参考文献：
  名称：

  环氧喹诺尔A，B和C和环氧维醇A的全合成以及Diels-Alder反应中2 H-吡喃衍生物作为二烯组分的反应性

  摘要：

  描述了环氧喹啉A，B和C以及环氧双酚A（RKB-3564D）的全合成的两种形式的全部细节。在第一代合成中，HfCl 4介导的呋喃与科里的手性助剂的非对映选择性Diels-Alder反应已得到开发。在第二代合成中，开发了一种无色谱法制备碘代内酯的方法，该方法通过使用丙烯酰氯作为呋喃的Diels-Alder反应中的亲二烯体，并开发了由脂肪酶介导的环己烯醇衍生物的动力学拆分方法。第二代合成适合大规模制备。仿生级联反应涉及氧化，6π-电环化，然后Diels-Alder二聚化是环氧喹诺醇A，B和C的复杂七环结构形成的关键反应。 6π-电环化和正式的[4 + 4]环加成反应。2小时由氧化/6π-电环化生成的β-吡喃起良好的二烯作用，可与数个亲二烯体反应，一步生成多环化合物。氮杂五环化合物通过类似的级联反应合成，该级联反应由四个连续步骤组成：氧化，亚胺形成，6π-氮杂电子环化和Diels-Alder二聚化。

  DOI：

  10.1021/jo048425h
• 作为产物：
  描述：

  methyl 3-deoxyshikimate 在 N-溴代丁二酰亚胺(NBS) 、 phosphate buffer 、 phosphorus pentoxide 、 sodium carbonate 、 sodium bromide 作用下， 以 丙酮 为溶剂， 反应 8.83h， 生成 rac-(1R,5R,6S)-3-methoxycarbonyl-7-oxabicyclo[4.1.0]hept-2-en-5-ol
  参考文献：
  名称：

  Fex, Tomas; Trofast, Jan; Wickberg, Boerje, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1981, vol. 35, # 2, p. 91 - 96

  摘要：

  DOI：

文献信息

• A practical total synthesis of both enantiomers of epoxyquinols A and B
  作者：Mitsuru Shoji、Satoshi Kishida、Mitsuhiro Takeda、Hideaki Kakeya、Hiroyuki Osada、Yujiro Hayashi

  DOI：10.1016/s0040-4039(02)02271-2

  日期：2002.12

  practical total synthesis of both enantiomers of epoxyquinols A and B has been developed. Key reactions are the chromatography-free preparation of an iodolactone by using acryloyl chloride as dienophile in the Diels–Alder reaction of furan, the lipase-mediated kinetic resolution of a cyclohexenol derivative, and a modified procedure for α-iodonation of a cyclohexenone.

  已经开发了环氧喹诺醇A和B的两种对映异构体的实用全合成。关键反应是在呋喃的Diels-Alder反应中使用丙烯酰氯作为亲二烯体，通过无色谱法制备碘内酯，通过环己烯醇衍生物的脂肪酶介导的动力学拆分，以及用于环己烯酮的α-碘化反应的改进方法。
• Total synthesis of racemic chorismic acid and (-)-5-enolpyruvylshikimic acid ("compound Z1")
  作者：Donald A. McGowan、Glenn A. Berchtold

  DOI：10.1021/ja00389a025

  日期：1982.12
• Rajapaksa, D.; Keay, B. A.; Rodrigo, R., Canadian Journal of Chemistry, 1984, vol. 62, p. 826 - 828
  作者：Rajapaksa, D.、Keay, B. A.、Rodrigo, R.

  DOI：——

  日期：——
• Lipase-catalyzed enantio- and regioselective transformation of 3-epi-shikimic acid derivatives as the key step for the entry of polyoxygenated carbacycles
  作者：Manabu Hamada、Toshinori Higashi、Mitsuru Shoji、Kazuo Umezawa、Takeshi Sugai

  DOI：10.1016/j.molcatb.2010.07.009

  日期：2010.11

  Candida antarctica lipase B (Novozym 435)-catalyzed transesterification on methyl (+/-)-3,4-di-O-acetyl-5-O-(tert-butyldimethyl)silyl-3-epi-shikimate worked highly regio- and enantioselective manner. Only (3R,4S,5S)-isomer reacted with an E value over 500, exclusively on C-3 acetate. The regio- and enantioselectivity were greatly affected by the substitution pattern on the hydroxy groups. Towards polyoxygenated carbacycles, the above-mentioned highly selective transformation enabled the subsequent stereoselective inversion and dihydroxylation, to give methyl (3S,4R,5S)-3,4,5-triacetoxy-1-cyclohexenecarboxylate [antipode of naturally occurring methyl (-)-3,4,5-tri-O-acetylshikimate], and methyl (1R,2S,3S,4R,5R)-3,4-diacetoxy-5-(tert-butyldirnethyl)silyloxy-1,2-dihydroxy-cyclohexanecarboxylate. (C) 2010 Elsevier B.V. All rights reserved.
• Novel non-peptide inhibitors targeting death receptor-Mediated apoptosis
  作者：Hideaki Kakeya、Yasunobu Miyake、Mitsuru Shoji、Satoshi Kishida、Yujiro Hayashi、Takao Kataoka、Hiroyuki Osada

  DOI：10.1016/j.bmcl.2003.08.003

  日期：2003.11

  We have previously reported that ECH, (2R, 3R, 4S)-2,3-epoxy-4-hydroxy-5-hydroxymethyl-6-(1E)-propenyl-cyclohex-5-en-1-one inhibits Fas-mediated apoptosis by blocking self-activation of pro-caspase-8 in the death-inducing signaling complex (DISC). A series of ECH derivatives were asymmetrically synthesized via key synthetic intermediates obtained from lipase-catalyzed kinetic resolution. Inhibitory activities of the derivatives towards death receptor-mediated apoptosis both in type I and type 11 cells were investigated, revealing that novel non-peptide inhibitors, RKTS-33 and RKTS-34, are effective as ECH. (C) 2003 Elsevier Ltd. All rights reserved.