(3aR,7aS)-2,2-dimethyltetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol | 86795-44-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (3aR,7aS)-2,2-dimethyltetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol
• 英文别名: I+/--D-erythro-Pentopyranose, 2-deoxy-3,4-O-(1-methylethylidene)-；(3aR,6S,7aS)-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-ol
• CAS: 86795-44-0
• 化学式: C₈H₁₄O₄
• 分子量: 174.197
• InChiKey: HFPIQGCIXRKIGK-XVMARJQXSA-N

物化性质

• 沸点：
  274.6±40.0 °C(Predicted)
• 密度：
  1.167±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3aR,7aS)-2,2-dimethyltetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol 在 正丁基锂 、 甲基三苯基碘化膦 、 三氧化硫吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 1.0h， 生成 (E)-methyl 3-((4R,5S)-5-allyl-2,2-dimethyl-1,3-dioxolan-4-yl)acrylate
  参考文献：
  名称：

  Minimal Fluorous Tagging Strategy that Enables the Synthesis of the Complete Stereoisomer Library of SCH725674 Macrolactones

  摘要：

  Four mixtures of four fluorous-tagged quasiisomers have been synthesized, demixed, and detagged to make all 16 stereoisomers of the macrocyclic lactone natural product Sch725674. A new bare-minimum tagging pattern needs only two tags one fluorous and one nonfluorous-to encode four isomers. The structure of Sch725674 is assigned as (5R,6S,8R,14R,E)-5,6,8-trihydroxy-14-pentyloxacyclotetradec-3-en-2-one. Various comparisons of spectra of 32 lactones (16 with tags, 16 without) and 16 ester precursors (8 with tags, 8 without) provide insights into when and why related compounds have the same or different spectra.

  DOI：

  10.1021/ja302260d
• 作为产物：
  描述：

  2-deoxy-D-ribose 、 2-甲氧基丙烯 在 4-甲基苯磺酸吡啶 作用下， 以 乙酸乙酯 为溶剂， 反应 15.0h， 生成 (3aR,7aS)-2,2-dimethyltetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol 、 (3aR,7aS)-2,2-dimethyltetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol
  参考文献：
  名称：

  巨噬细胞衍生的抗炎和可分解脂质介体Maresin 2的首次全合成

  摘要：

  源自二十二碳六烯酸的强效抗炎脂质介体Maresin 2的首次全合成已经实现。手性羟基基团的C13和C14是从经由手性池策略得到3,4- ö异丙叉-2-脱氧d -核糖。Wittig反应和丙酮化物裂解，然后轻度酯水解，得到Maresin 2。

  DOI：

  10.1016/j.tetlet.2014.11.082

文献信息

• Iron‐Catalyzed Radical Cleavage/C−C Bond Formation of Acetal‐Derived Alkylsilyl Peroxides
  作者：Yoko Shiozaki、Shunya Sakurai、Ryu Sakamoto、Akira Matsumoto、Keiji Maruoka

  DOI：10.1002/asia.201901695

  日期：2020.3.2

  selective cleavage of acetal-derived alkylsilyl peroxides, followed by the formation of a carbon-carbon bond is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the acetal moiety and the carbon electrophile. Mechanistic studies suggest that the present reaction proceeds through a free-radical process involving carbon radicals generated

  报道了一种基于自由基的新颖方法，用于铁催化的乙缩醛衍生的烷基甲硅烷基过氧化物的选择性裂解，然后形成碳-碳键。反应在温和的反应条件下进行，并且相对于缩醛部分和亲电碳表现出宽泛的底物范围。机理研究表明，本反应通过自由基过程进行，该自由基过程涉及由乙缩醛部分内碳-碳键的均相裂解产生的碳自由基。还描述了该方法在糖衍生的烷基甲硅烷基过氧化物中的合成应用。
• Synthesis and Biological Evaluation of Bicyclo[1.1.1]pentane-Containing Aromatic Lipoxin A₄ Analogues
  作者：Benjamin Owen、Monica de Gaetano、Andrew Gaffney、Catherine Godson、Patrick J. Guiry

  DOI：10.1021/acs.orglett.2c02345

  日期：2022.8.19

  Bicyclo[1.1.1]pentanes (BCPs) are potential isosteric replacements for arenes and/or alkyl groups within drug candidates. We carried out an asymmetric synthesis of four BCP-containing synthetic lipoxin A4 mimetics (BCP-sLXms) in which the key steps were a Suzuki coupling, an asymmetric ketone reduction, and a triethylborane-initiated radical bicyclopentylation. These mimetics were screened for their impact

  脂氧素是炎症消退的重要驱动因素，表明潜在的治疗益处。双环[1.1.1]戊烷 (BCP) 是候选药物中芳烃和/或烷基的潜在等排替代品。我们对四种含有 BCP 的合成脂氧素 A 4模拟物 (BCP-sLXms)进行了不对称合成，其中关键步骤是 Suzuki 偶联、不对称酮还原和三乙基硼烷引发的自由基双环戊基化。筛选了这些模拟物对炎症反应的影响，发现一种咪唑-BCP-sLXm ( 6a ) 具有高抗炎活性。
• A general synthesis of aromatic and heteroaromatic lipoxin B₄ analogues
  作者：Benjamin Owen、Patrick J. Guiry

  DOI：10.1039/d3ob01076g

  日期：——

  Lipoxins are an important class of pro-resolving mediators that play a crucial role in the resolution of inflammation. Thus, the synthesis of more chemically and metabolically stable synthetic lipoxin analogues is an area of significant interest. Whereas synthetic analogues of lipoxin A4 (LXA4) have been well studied, analogues of lipoxin B4 (LXB4) have been the focus of considerably less attention

  脂氧素是一类重要的促消退介质，在炎症消退中发挥着至关重要的作用。因此，合成化学和代谢更稳定的合成脂氧素类似物是一个令人感兴趣的领域。虽然脂氧素 A 4 (LXA 4 )的合成类似物已得到充分研究，但脂氧素 B 4 (LXB 4 )类似物却受到较少关注。在此，我们报告了 LXB 4模拟物的重点库的不对称合成，其中分子的三烯核心已被不同的芳香环和杂芳香环取代。这些类似物的合成都是通过通用策略实现的，其中关键步骤是共同上链片段和芳香族下链之间的铃木交叉偶联，然后是立体选择性酮还原。
• Synthesis of a Bicyclo[1.1.1]pentane‐Containing Aromatic Lipoxin B₄ Analogue and Heteroaromatic Congeners
  作者：Benjamin Owen、Patrick J. Guiry

  DOI：10.1002/ejoc.202400256

  日期：——

  This work describes the asymmetric synthesis of an aromatic analogue of lipoxin B4 containing a conformationally rigid and potentially more metabolically resistant bicyclo[1.1.1]pentane (BCP) ring incorporated into the upper alkyl chain. This was achieved via the design of a key BCP-containing fragment that could be used as a common intermediate in the synthesis of the target analogue as well as other

  这项工作描述了脂氧素 B 4 的芳香族类似物的不对称合成，该类似物包含构象刚性且可能更具代谢耐受性的双环[1.1.1]戊烷 (BCP) 环并入上部烷基链中。这是通过设计一个包含 BCP 的关键片段来实现的，该片段可用作合成目标类似物以及其他杂芳族同系物的通用中间体。
• Synthesis of Bifunctional Lipoxin‐Derived Enzyme‐Triggered CO‐Releasing Molecules (LipET‐CORMs)
  作者：Lars Hemmersbach、Ruth Adam、Christina Plevnali、Xinmiao Zhang、Benito Yard、Hans‐Günther Schmalz

  DOI：10.1002/ejoc.202201424

  日期：2023.3

  AbstractIn an attempt to develop new anti‐inflammatory agents which act by co‐release of carbon monoxide (CO) and a specialized pro‐resolving mediator, we designed conjugates of a lipoxin A4 analogue and an acyloxycyclohexadiene‐Fe(CO)3 complex as an esterase‐triggered CO‐releasing molecule (ET‐CORM). After adjustment of the protecting group strategy, two of such compounds were successfully prepared by total synthesis (12 steps; 4–5 % overall yield) starting from deoxy‐d‐ribose and exploiting a Wittig olefination and an intermolecular Heck reaction as key C−C bond‐forming steps. A crucial late reduction of an aryl‐ketone moiety in the presence of a highly sensitive dienol ester functionality was achieved with BH3‐SMe2 in the presence of catalytic amounts of NaBH4. Both target compounds were dose‐dependently toxic towards cultured human umbilical vein endothelial cells (HUVEC), with LipET‐CORM 1‐A being slightly more toxic. While induction of heme oxygenase 1 (HO‐1) in HUVEC was observed for both compounds, they did not inhibit TNF‐α‐mediated VCAM‐1 expression in these cells. In M2 polarized macrophages HO‐1 expression was more pronounced as compared to M1 polarized macrophages. In both types of macrophages HO‐1 expression was downregulated by lipopolysaccharide, but only in M2 macrophages HO‐1 expression was rescued by LipET‐CORM. 15‐Lipoxygenase (15‐LO) was only expressed in M2 macrophages and was not influenced by LipET‐CORM. Collectively our data demonstrate that LipET‐CORMs induce HO‐1 expression in endothelial cells and M2 polarized macrophages. The role of the intra‐cellular released lipoxin A4 in resolution of inflammation, however, remains to be assessed.