(3R,3AS,6AS)-3-羟基甲基-3,3A,4,6A四氢-2H-环戊二烯并[B]呋喃-2-酮 | 148555-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 中文名称: (3R,3AS,6AS)-3-羟基甲基-3,3A,4,6A四氢-2H-环戊二烯并[B]呋喃-2-酮
• 英文名称: (+)-(3R,3aS,6aS)-3-hydroxy-3,3a,6,6a-tetrahydro-cyclopenta[b]furan-2-one
• 英文别名: (3R,3aS,6aS)-3-hydroxy-3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one；(3R,3aS,6aS)-3-hydroxy-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one
• CAS: 148555-10-6
• 化学式: C₇H₈O₃
• 分子量: 140.139
• InChiKey: LOTRXPYWDQSASJ-NGJCXOISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,3AS,6AS)-3-羟基甲基-3,3A,4,6A四氢-2H-环戊二烯并[B]呋喃-2-酮 在 盐酸 、 4-二甲氨基吡啶 、 lithium hydroxide 、 2,4,6-三氯苯甲酰氯 、 四氯化钛 、 二异丁基氢化铝 、 碳酸氢钠 、 potassium tri-sec-butyl-borohydride 、 对甲苯磺酸 、 N,N-二异丙基乙胺 、 硫脲 、 三苯基膦 、 pyridinium chlorochromate 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 生成 布雷非德菌素 A
  参考文献：
  名称：

  Facile synthesis of (+)-brefeldin a utilizing two optically active synthons prepared by different enzyme-catalysed reactions

  摘要：

  内酯 4a 和醇 6（均可以通过生物催化过程以旋光形式获得）已被用作合成子用于制备 (+)-布雷菲德菌素 A。

  DOI：

  10.1039/c39940001085
• 作为产物：
  描述：

  (3S,3aR,6aR)-3a,4-dihydro-3-hydroxy-3H-cyclopenta[b]furan-2(6aH)-one 在 吡啶 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (3R,3AS,6AS)-3-羟基甲基-3,3A,4,6A四氢-2H-环戊二烯并[B]呋喃-2-酮
  参考文献：
  名称：

  具有合成意义的双环羟基内酯的便捷化学拆分

  摘要：

  通过用（S）-O-乙酰丙酰氯处理来拆分容易获得的双环内酯1，得到可分离的非对映异构体对（-）- 3和（-）- 4，其各自的构型由进行的X射线晶体学推论得出在溴衍生物（-）- 5上。

  DOI：

  10.1016/0040-4039(94)88268-1

文献信息

• Conversion of (–)-4-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one into the anti-HIV agent carbovir
  作者：Rosemary A. MacKeith、Ray McCague、Horacio F. Olivo、Christopher F. Palmer、Stanley M. Roberts

  DOI：10.1039/p19930000313

  日期：——

  The lactone (±)-1 was resolved using Pseudomonas fluorescens lipase and vinyl acetate; the ester (–)-3 obtained by this process was subsequently converted into the anti-HIV agent carbovir (–)-9.

  使用荧光假单胞菌脂肪酶和乙酸乙烯酯拆分内酯（±）-1。随后将通过此方法获得的酯（–）- 3转化为抗HIV药剂carbovir（–）- 9。
• First enantioselective synthesis of (+)-(3R,3aS,6aS)-3-hydroxy-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one — a versatile chiral heterocyclic building block
  作者：Steffen Kudis、Günter Helmchen

  DOI：10.1016/s0040-4020(98)00497-9

  日期：1998.8

  phosphinooxazoline 2 as chiral ligand enantiomeric excess of > 99% and > 90% yield were obtained. Alkylation products were transformed in three steps to (+)-(3R,3aS,6aS)-3-hydroxy-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one (1a) in up to 52 % yield.

  描述了2-乙酰氧基丙二酸酯与2-环戊烯基氯的不对称Pd催化的烯丙基烷基化。使用基于环丙三烯的膦酰基恶唑啉2作为手性配体，对映体过量＞ 99％，＞ 90％。将烷基化产物分三步转化为（+）-（3R，3aS，6aS）-3-羟基-3,3a，4,6a-四氢环戊[b]呋喃-2-酮（1a），收率高达52％ 。
• Synthesis of optically active bicyclic lactone building blocks using catalytic enantioselective glyoxylate-ene reaction
  作者：Nicholas Gathergood、Karl Anker Jørgensen

  DOI：10.1039/a905637h

  日期：——

  A new catalytic approach for the formation of optically active bicyclic lactones applying an enantioselective glyoxylate-ene reaction is presented; the catalytic reaction proceeds with formation of the two key stereogenic centers in good yield and with high diastereo- and enantio-selectivity.

  本文介绍了一种利用对映选择性乙醛酸烯反应生成光学活性双环内酯的新催化方法；催化反应以良好的收率和较高的非对映及对映选择性进行，并形成了两个关键的立体中心。
• Synthesis of (+)-brefeldin-A
  作者：Andrew J. Carnell、Guy Casy、Gilles Gorins、Arefeh Kompany-Saeid、Ray McCague、Horacio F. Olivo、Stanley M. Roberts、Andrew J. Willetts

  DOI：10.1039/p19940003431

  日期：——

  Two routes to (+)-brefeldin A have been investigated. In one the bicyclic ketone 2 was transformed into the hydroxy lactone 7. Subsequent reduction, opening of the heterocyclic ring and epimerization furnished the aldehyde 13. Further steps towards the natural product from this late stage intermediate 13 were not investigated. in the second route, the readily available hydroxy lactone 17 was converted into the enone 22. Conjugate addition of the requisite cuprate reagent to this enone afforded the 3,4-disubstituted cyclopentanone 24 which was converted into brefeldin-A 29 in five steps.
• Nucleosides and Nucleotides. 173. Synthesis of Cyclic IDP-carbocyclic-ribose, a Stable Mimic of Cyclic ADP-ribose. Significant Facilitation of the Intramolecular Condensation Reaction of <i>N</i>-1-(Carbocyclic-ribosyl)inosine 5‘,6‘‘-Diphosphate Derivatives by an 8-Bromo-Substitution at the Hypoxanthine Moiety
  作者：Satoshi Shuto、Michiyo Shirato、Yuji Sumita、Yoshihito Ueno、Akira Matsuda

  DOI：10.1021/jo9717797

  日期：1998.3.1

  Cyclic ADP-ribose (cADPR, 1) is a general mediator involved in cellular Ca2+ signaling. However, both the biological and chemical instability of cADPR limit studies on its physiological role. We designed cyclic ADP-carbocyclic-ribose (3) and its inosine congener 4 as stable mimics of cADPR and successfully synthesized 4. Starting with cyclopentadiene, the optically active carbocyclic unit 8 was constructed via enzymatic optical resolution. S(N)2 reactions of 8 with inosine derivative 7 and the 8-bromoinosine derivative 25 gave the N-1-substituted derivatives 6 and 26, which were converted to the corresponding diphosphate derivatives 5 and 22. The intramolecular condensation reactions between the two phosphate groups of 5 and 22 were investigated, Although the reaction with inosine derivative 5 did not produce any of the cyclization product 20, treatment of the corresponding 8-bromoinosine derivative 22 with EDC gave the desired intramolecular condensation product 29 in 23% yield. Thus, the significant effect of the 8-bromo group at the hypoxanthine moiety in facilitating the key intramolecular condensation reaction between the phosphate groups of the substrate 22 was recognized. This is possibly due to conformational restriction of the molecule in a syn-form around its glycosyl linkage. The 8-bromo and isopropylidene groups were removed in succession to give the target compound 4. This is the first total synthesis of this type of cyclic nucleotide.