3-(7-Methyl-1,4-dioxaspiro[4.5]decan-7-yl)propanal | 127488-39-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(7-Methyl-1,4-dioxaspiro[4.5]decan-7-yl)propanal
• CAS: 127488-39-5
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: UYRLFHHRMRKMOS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(7-Methyl-1,4-dioxaspiro[4.5]decan-7-yl)propanal 在 palladium on activated charcoal 四氢吡咯 、 盐酸 、 lithium aluminium tetrahydride 、 jones reagent 、 氢气 、 溶剂黄146 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 乙酸乙酯 、 丙酮 为溶剂， -78.0~25.0 ℃ 、275.79 kPa 条件下， 反应 49.0h， 生成 (αR^*,1R^*,3aR^*,7aS^*)-Hexahydro-α-isopropyl-3a-methyl-7-methylene-1-indanacetic acid
  参考文献：
  名称：

  Synthetic approaches to the axane family of sesquiterpenoids. Total synthesis of (dl)-axamide-4, (dl)-axisonitrile-4, and (dl)-axisothiocyanate-4

  摘要：

  Two methods for the preparation of perhydroindan 7 are described. One involves an intramolecular free radical cyclization in a key step and proceeds in 13 steps and 9% yield from anisole (9). The other involves an intramolecular conjugate addition mediated by pyrrolidine (28 --> 7) and proceeds in five steps and 30% overall yield from vinylogous ester 29. Two unsuccessful attempts to convert 7 into axane sesquiterpenoids 1-6 are described. The synthesis of axanes 4-6 was achieved using a potassium tert-butoxide catalyzed cyclization of a dienoic keto ester as a key step (47 + 48 --> 49). Conversion of alpha,beta-unsaturated ester 49 to vinyl isocyanate 57 was accomplished using a Curtius rearrangement and reduction of 57 with lithium triethylborohydride completed the synthesis of axamide-4 (4). The preparation of axisonitrile-4 (5) and axisothiocyanate-4 (6) from 4 is also described.

  DOI：

  10.1021/jo00033a023
• 作为产物：
  描述：

  3-(4-methylpent-3-enyl)cyclohex-2-enone 在 二甲基硫 、 碳酸氢钠 、 对甲苯磺酸 、 臭氧 、 原甲酸三甲酯 作用下， 以 乙醚 、 苯 为溶剂， 反应 20.8h， 生成 3-(7-Methyl-1,4-dioxaspiro[4.5]decan-7-yl)propanal
  参考文献：
  名称：

  通过分子内共轭加成合成碳环化合物：黄烷倍半萜的总合成。

  摘要：

  描述了（+/-）-ax酰胺-1（2）和（+/-）-轴腈-1（1）的合成。合成需要分别从乙烯基酯8到12步和13步，并且具有不饱和酯7到非氢茚满5的非对映选择性环化的特点。还描述了一些有趣的有机金属化合物的反应，这些有机金属化合物来自[[（三甲基甲硅烷基）甲基]氯化镁和三氯化铈。 。

  DOI：

  10.1021/jo951532e

文献信息

• Total Synthesis of Allocyathin B₂, a Metabolite of Bird's Nest Fungi
  作者：Motoo Tori、Naoko Toyoda、Masakazu Sono

  DOI：10.1021/jo971514s

  日期：1998.1.1

  Allocyathin B-2 has been synthesized using aldol reactions for construction of rings A and B, introduction of the side chain for ring B, cyclization of the acetyl group into a lactone, and construction of the seven-membered diene aldehyde during the last step.
• Synthesis of Carbocycles via Intramolecular Conjugate Additions: Another Solution to the Terpenoid Side Chain Stereochemistry Problem
  作者：Alyx-Caroline Guevel、David J. Hart

  DOI：10.1021/jo951531m

  日期：1996.1.1

  Intramolecular conjugate additions of keto esters 7-11, mediated by pyrrolidine-acetic acid, provide perhydroindans or bicyclo[6.3.0]undecanes with high levels of diastereoselectivity at the acyclic stereogenic center. Levels of acyclic diastereoselection depend on starting unsaturated ester olefin geometry.
• HART, DAVID J.;LAI, CHIN-SHAN, SYNLETT.,(1989) N, C. 49-51
  作者：HART, DAVID J.、LAI, CHIN-SHAN

  DOI：——

  日期：——
• Synthesis of Carbocycles via Intramolecular Conjugate Additions:  Total Syntheses of Axane Sesquiterpenoids
  作者：Alyx-Caroline Guevel、David J. Hart

  DOI：10.1021/jo951532e

  日期：1996.1.1

  Syntheses of (+/-)-axamide-1 (2) and (+/-)-axisonitrile-1 (1) are described. The syntheses require 12 steps and 13 steps, respectively, from vinylogous ester 8 and feature the diastereoselective cyclization of unsaturated ester 7 to perhydroindan 5. Some interesting reactions of the organometallic derived from [(trimethylsilyl)methyl]magnesium chloride and cerium trichloride are also described.

  描述了（+/-）-ax酰胺-1（2）和（+/-）-轴腈-1（1）的合成。合成需要分别从乙烯基酯8到12步和13步，并且具有不饱和酯7到非氢茚满5的非对映选择性环化的特点。还描述了一些有趣的有机金属化合物的反应，这些有机金属化合物来自[[（三甲基甲硅烷基）甲基]氯化镁和三氯化铈。 。
• Synthetic approaches to the axane family of sesquiterpenoids. Total synthesis of (dl)-axamide-4, (dl)-axisonitrile-4, and (dl)-axisothiocyanate-4
  作者：Balan Chenera、Che Ping Chuang、David J. Hart、Chin Shan Lai

  DOI：10.1021/jo00033a023

  日期：1992.3

  Two methods for the preparation of perhydroindan 7 are described. One involves an intramolecular free radical cyclization in a key step and proceeds in 13 steps and 9% yield from anisole (9). The other involves an intramolecular conjugate addition mediated by pyrrolidine (28 --> 7) and proceeds in five steps and 30% overall yield from vinylogous ester 29. Two unsuccessful attempts to convert 7 into axane sesquiterpenoids 1-6 are described. The synthesis of axanes 4-6 was achieved using a potassium tert-butoxide catalyzed cyclization of a dienoic keto ester as a key step (47 + 48 --> 49). Conversion of alpha,beta-unsaturated ester 49 to vinyl isocyanate 57 was accomplished using a Curtius rearrangement and reduction of 57 with lithium triethylborohydride completed the synthesis of axamide-4 (4). The preparation of axisonitrile-4 (5) and axisothiocyanate-4 (6) from 4 is also described.