2,2'-(methylene)bis-(1-hydroxycyclohex-1-en-3-one) | 16807-61-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2'-(methylene)bis-(1-hydroxycyclohex-1-en-3-one)
• 英文别名: 2,2'-(ethane-1,1-diyl)bis(3-hydroxycyclohex-2-enone)；3-Hydroxy-2-[1-(2-hydroxy-6-oxocyclohexen-1-yl)ethyl]cyclohex-2-en-1-one
• CAS: 16807-61-7
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: PVSUNSJAZMCVLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-二苯乙烯 、 2,2'-(methylene)bis-(1-hydroxycyclohex-1-en-3-one) 在 manganese(III) triacetate dihydrate 、 溶剂黄146 、 (4aS,9S,9aS)-12,12-bis(4-methylphenyl)-9-methyl--3,4,5,6,7,9-hexahydro-8H-4a,9a-(epoxyethano)xanthene-1,8(2H)-dione 作用下， 以44 %的产率得到(4aR,9S,9aR)-9-methyl-12,12-diphenyl-3,4,5,6,7,9-hexahydro-8H-4a,9a-(epoxyethano)-xanthene-1,8(2H)-dione
  参考文献：
  名称：

  Synthesis of dioxapropellanes using Mn(III)-based oxidative tandem cyclization of tetracarbonyl compounds with diarylethenes

  摘要：

  摘要 基于锰（III）的四羰基化合物与 1,1-二叔丁烯的氧化反应生成了二氧丙环。使用亚甲基双（3-羟基环己-2-烯-1-酮）作为四羰基化合物，可以生产出 3,4,5,6,7,9-六氢-8H-4a,9a-(环氧乙烷)氧杂蒽-1,8(2H)-二酮，收率很高。虽然该反应与自环化反应竞争生成 3,5,6,7-四氢-4H-螺[苯并呋喃-2,1′-环己烷]-2′,4,6′-三酮，但在室温下加入辅助溶剂甲酸可以控制反应。烷基和芳基取代的亚甲基双（3-羟基环己-2-烯-1-酮）反应生成相应的非对映混合物二氧丙环。形成非对映异构体的原因是串联环化过程中中间碳位的立体阻碍。使用 2-(2-羟基-4,4-二甲基-6-氧代环己-1-烯-1-基)丁烷-1,4-二酮和 2,2′-亚甲基双(3-羟基环戊-2-烯-1-酮)的反应也产生了相应的二氧杂环丙烷。本文讨论了生成物的结构测定和二氧杂环戊烷的生成反应途径。

  DOI：

  10.1093/bulcsj/uoae011
• 作为产物：
  描述：

  1,3-环己二酮 在 Candida parapsilosis ATCC 7330 whole cells 作用下， 以 乙醇 、 水 为溶剂， 反应 4.0h， 以42%的产率得到2,2'-(methylene)bis-(1-hydroxycyclohex-1-en-3-one)
  参考文献：
  名称：

  Regio- and enantioselective reduction of diketones: preparation of enantiomerically pure hydroxy ketones catalysed by Candida parapsilosis ATCC 7330

  摘要：

  Enantiomerically enriched hydroxy ketones were prepared by the reduction of the corresponding diketones with excellent enantiomeric excess (98%) and in good yields (up to 75%) using whole cells of Candida parapsilosis ATCC 7330. Cyclic diketones, such as 1,2-cyclohexanedione and 1,4-cyclohexanedione, resulted in hydroxy ketones as products. Cyclohexane-1,3-dione and 5,5-dimethylcyclohexane1,3-dione gave dimerised products, such as 2,2'-(ethane-1,1-diy1)bis(3-hydroxycyclohex-2-enone) and 2,2'-(ethane-1,1-diy1)bis(3-hydroxy-5,5-dimethylcyclohex-2-enone) with acetaldehyde generated in situ from whole cells of Candida parapsilosis ATCC 7330, which is reported here for the first time. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.09.001

文献信息

• Organocatalytic Sequential One-Pot Double Cascade Asymmetric Synthesis of Wieland−Miescher Ketone Analogues from a Knoevenagel/Hydrogenation/Robinson Annulation Sequence:  Scope and Applications of Organocatalytic Biomimetic Reductions
  作者：Dhevalapally B. Ramachary、Mamillapalli Kishor

  DOI：10.1021/jo070277i

  日期：2007.7.1

  practical and novel organocatalytic chemo- and enantioselective process for the cascade synthesis of highly substituted 2-alkyl-cyclohexane-1,3-diones and Wieland−Miescher (W−M) ketone analogs is presented via reductive alkylation as a key step. First time, we developed the one-step alkylation of dimedone and 1,3-cyclohexanedione with aldehydes and Hantzsch ester through an organocatalytic reductive alkylation

  通过还原烷基化，提出了一种实用且新颖的有机催化化学和对映选择性工艺，用于级联合成高度取代的2-烷基-环己烷-1,3-二酮和Wieland-Miescher（WM）酮类似物，这是关键步骤。首次，我们通过有机催化还原烷基化策略开发了二醛和1,3-环己二酮与醛和Hantzsch酯的一步烷基化。l的直接组合CH酸（二甲酮和1,3-环己烷二酮），醛，汉茨sch酯和甲基乙烯基酮的脯氨酸催化的级联Knoevenagel /加氢和级联的Robinson环氧化反应提供了高官能度的W-M酮类似物，并具有良好的收率。优异的对映选择性。许多还原性烷基化产物直接显示在药物化学中。
• A synthetic entry into fused pyran derivatives through carbon transfer reactions of 1,3-oxazinanes and oxazolidines with carbon nucleophiles
  作者：Kamaljit Singh、Jasbir Singh、Harjit Singh

  DOI：10.1016/0040-4020(96)00879-4

  日期：1996.11

  of various 2 substituted 1,3-oxazinanes 3 and 1,3-oxazolidines 4 with cyclic carbon nucleophiles viz. 5,5-dimethyl-1,3-cyclohexanedione and 1,3-cyclohexanedione furnish xanthene derivatives, whereas a Knoevenagel reaction proceeds with acyclic nucleophiles. In case of 4b and 4c, a unique synthesis of functionalised α-tetralones has emerged. Reactions of mixtures of cyclic and acyclic carbon nucleophiles

  各种2个取代的1,3-恶嗪并3和1,3-恶唑烷4与环状碳亲核试剂的酸催化缩合。5,5-二甲基-1,3-环己二酮和1,3-环己二酮提供了x吨衍生物，而Knoevenagel反应则与无环亲核试剂一起进行。在4b和4c的情况下，出现了功能化的α-四氢萘酮的独特合成。环状和无环碳亲核试剂与3的混合物的反应提供了一些官能化的且部分还原的苯并吡喃衍生物。
• Visible Light Mediated Organophotoredox Catalyzed Synthesis of Tetraketones Using Tertiary Amines as Alkyl Synthons
  作者：Shankhajit Mondal、Akanksha M. Pandey、Boopathy Gnanaprakasam

  DOI：10.1021/acs.joc.3c02613

  日期：2024.3.15

  tetraketones using cyclic-1,3-diketones and tertiary amines as alkyl synthons under 18 W blue LED have been accomplished. The condition is very mild that uses air as a green oxidant and avoids previously used harsh conditions like high temperature. Diverse arrays of tertiary amines first undergo reductive quenching of excited photocatalysts to form iminium ions that upon subsequent attack by cyclic-1,3-diketones

  在 18 W 蓝光 LED 下，使用环 1,3-二酮和叔胺作为烷基合成子，曙红 Y 催化合成具有生物活性的四酮。条件非常温和，使用空气作为绿色氧化剂，避免了以前使用的高温等恶劣条件。各种叔胺首先对激发的光催化剂进行还原猝灭，形成亚胺离子，随后受到环 1,3-二酮的攻击，产生四酮。该方法通过 31 个实例进行了验证，收率高达 76%。还通过重要的例子证明了在曙红 Y 催化剂存在下在太阳条件下该反应的可行性。
• Access to Protected 2-Alkylidene 1,3-diones by Modified Knoevenagel Reaction in the Presence of Thiophenol. A New Approach to Spirocyclopentanol Construction
  作者：Klaus Fuchs、Leo A. Paquette

  DOI：10.1021/jo00082a007

  日期：1994.2

  A general procedure is described for trapping the products of Knoevenagel condensation involving 1,3-diketones and aliphatic aldehydes. Simple stirring of a three-component mixture consisting of each reactant and thiophenol in dichloromethane containing silica gel leads to products in which the 2-alkylidene 1,3-dione has been intercepted to give a (most often) crystalline Michael adduct. The yields are usually quite acceptable, especially if the beta-dicarbonyl compound is cyclic. Oxidation of these adducts with sodium periodate regenerates the conjugated enedione, which reacts rapidly with air to give a cyclic peroxide unless protected from the atmosphere. When a monoprotected succinaldehyde is utilized as starting material, hydrolysis of the resultant adduct in aqueous acid results in intramolecular aldolization to give a spirocyclic cyclopentanol.
• Chemistry of acetals
  作者：Zh. A. Krasnaya、S. S. Yufit、V. F. Kucherov

  DOI：10.1007/bf01176036

  日期：1967.5