(+)-andirocalctone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (+)-andirocalctone
• 英文别名: (S)-4,8-dimethyl-1-oxaspiro[4.5]deca-3,7-dien-2-one；andirolactone；(5R)-4,8-dimethyl-1-oxaspiro[4.5]deca-3,7-dien-2-one
• 化学式: C₁₁H₁₄O₂
• 分子量: 178.231
• InChiKey: BDJHZBSSFOFAQX-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (-)-1,8-p-Menthadien-4-ol 在 titanium(IV) isopropylate 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 生成 (+)-andirocalctone
  参考文献：
  名称：

  First asymmetric synthesis of both enantiomers of andirolactone

  摘要：

  We have achieved the first asymmetric synthesis of (+)- and (-)-andirolactone. The key steps were separation of limonene oxide diastereomers, asymmetric oxidation induced by the chiral intermediate and ring-closing metathesis in the presence of catalytic amounts of Lewis acid to form the spirocyclic butenolides. (c) 2006 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2006.12.031

文献信息

• A protecting-group-free synthesis of arbusculone, andirolactone, pinnatolide, ipomolactone, cyclocapitelline and isocyclocapitelline
  作者：Srinivas Gajula、Madasu Madhu、Suresh Kumar Chintakrinda、J.S. Yadav、Debendra K. Mohapatra

  DOI：10.1016/j.tetlet.2018.10.024

  日期：2018.11

  A general approach for a collective synthesis of natural products containing substituted THF ring is described. In this paper, Arbusculone, a small molecule natural product accomplished using a short route, is used as the key intermediate to achieve the total synthesis of Andirolactone, Pinnatolide, Ipomolactone, Cyclocapitelline, Isocyclocapitelline and their two isomers in less than ten steps. The

  描述了用于集体合成含有取代的THF环的天然产物的一般方法。在本文中，使用短路径完成的小分子天然产物Arbusculone被用作关键中间体，可在不到十个步骤的情况下完成Andirolactone，Pinnatolide，Ipomolactone，Cyclocapitelline，Isocyclocapitelline及其两个异构体的全合成。目前的工作着重强调了无保护基团的全部合成方法，以及从市售廉价原料中获得这些天然产物的最短途径。
• Expanding the Chiral Monoterpene Pool: Enantioselective Diels–Alder Reactions of α-Acyloxy Enones
  作者：Skyler D. Mendoza、Michael Rombola、Yujia Tao、Stephan J. Zuend、Roland Götz、Martin J. McLaughlin、Sarah E. Reisman

  DOI：10.1021/acs.orglett.2c01343

  日期：2022.6.3

  α-acyloxy enones has been developed to synthesize chiral oxidized cyclohexenes. Yttrium(III) triflate, in conjunction with a chiral pyridinebisimidazoline (PyBim) ligand, was found to catalyze the asymmetric [4 + 2] cycloaddition with a variety of dienes and α-acyloxy enone dienophiles. Using this method, terpinene-4-ol, a key intermediate in the synthesis of commercial herbicide cinmethylin, can be prepared

  已经开发了 α-酰氧基烯酮的对映选择性 Diels-Alder (DA) 反应来合成手性氧化环己烯。发现三氟甲磺酸钇 (III) 与手性吡啶双咪唑啉 (PyBim) 配体一起催化与各种二烯和 α-酰氧基烯酮亲二烯体的不对称 [4 + 2] 环加成反应。使用该方法，可通过四步异戊二烯制备商业除草剂cinmethylin的关键中间体terpinene-4-ol。动力学数据和 NMR 研究的结合支持了一种机制，该机制涉及亲二烯体与钇催化剂的可逆结合，然后与二烯环加成作为速率决定步骤。
• First asymmetric synthesis of both enantiomers of andirolactone
  作者：Yi Li、Tao Zhang、Yu-Lin Li

  DOI：10.1016/j.tetlet.2006.12.031

  日期：2007.2

  We have achieved the first asymmetric synthesis of (+)- and (-)-andirolactone. The key steps were separation of limonene oxide diastereomers, asymmetric oxidation induced by the chiral intermediate and ring-closing metathesis in the presence of catalytic amounts of Lewis acid to form the spirocyclic butenolides. (c) 2006 Published by Elsevier Ltd.