(3aS,5aR,8aR,8bR)-5a-methyl-3a,4,5,5a-tetrahydro-1H-indeno[5,4-b]furan-2,8(8aH,8bH)-dione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3aS,5aR,8aR,8bR)-5a-methyl-3a,4,5,5a-tetrahydro-1H-indeno[5,4-b]furan-2,8(8aH,8bH)-dione
• 英文别名: (3aS,5aR,8aR,8bR)-5a-methyl-1,3a,4,5,8a,8b-hexahydrocyclopenta[e][1]benzofuran-2,8-dione
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: MAIFDZTVACEGFA-QZDOIJKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-bromo-6-methyl-1,5-heptadiene 、 (3aS,5aR,8aR,8bR)-5a-methyl-3a,4,5,5a-tetrahydro-1H-indeno[5,4-b]furan-2,8(8aH,8bH)-dione 在 叔丁基锂 、 copper(l) cyanide 、 三氟化硼乙醚 作用下， 以 乙醚 、 正戊烷 、 四氢呋喃 为溶剂， 反应 3.25h， 以51%的产率得到(3aS,5aR,6R,8aR,8bR)-5a-methyl-6-(6-methylhepta-1,5-dien-2-yl)-1,3a,4,5,6,7,8a,8b-octahydrocyclopenta[e][1]benzofuran-2,8-dione
  参考文献：
  名称：

  Total Synthesis of (±)-Aplykurodinone-1: Traceless Stereochemical Guidance

  摘要：

  The total synthesis of the highly degraded steroidal natural product, aplykurodinone-1 (1), has been accomplished. Key features include a one-flask hydrolysis/retro-aldol/iodolactonization sequence to excise the C-8 hydroxymethylene functionality with retention of stereochemistry and the stereoselective installation of the C-13 methyl group through hydrogenation with homogeneous catalyst.

  DOI：

  10.1021/ja1035495
• 作为产物：
  描述：

  5-羟基-2-戊酮 在 咪唑 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 四丙基高钌酸铵 、 草酰氯 、 bis(cyclopentadienyl)titanium (III) chloride 、 偶氮二异丁腈 、 L-(+)-酒石酸二异丙酯 、 cerium(III) chloride heptahydrate 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 碘 、 三甲基铝 、 三正丁基氢锡 、 palladium diacetate 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 125.83h， 生成 (3aS,5aR,8aR,8bR)-5a-methyl-3a,4,5,5a-tetrahydro-1H-indeno[5,4-b]furan-2,8(8aH,8bH)-dione
  参考文献：
  名称：

  Formal synthesis of degraded sterol (+)-aplykurodinone-1

  摘要：

  The formal synthesis of aplykurodinone-1 is accomplished starting from a suitably functionalized bicyclic lactone having the requisite cis-fused ring junction with a quaternary chiral center that was assembled following a Cp2TiCl-mediated radical cyclization protocol. Our synthetic route further elaborates implementation of Grubbs ring closing metathesis (RCM), Eschenmoser-Claisen rearrangement and iodo-lactonization reactions for the synthesis of the final tricyclic precursor of the target molecule. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.026

文献信息

• H-Bonding Mediated Asymmetric Intramolecular Diels–Alder Reaction in the Formal Synthesis of (+)-Aplykurodinone-1
  作者：Joon-Ho Lee、Cheon-Gyu Cho

  DOI：10.1021/acs.orglett.8b03250

  日期：2018.11.16

  stereochemical control element governing the π-facial selectivity of intramolecular Diels–Alder (IMDA) reaction of an enone tethered 2-pyrone. In the IMDA process, the configuration at a stereogenic, hydroxyl bearing an α-carbon in the enone dienophile is conveyed in a highly effective manner through intramolecular hydrogen bonding with the enone carbonyl oxygen. The tricyclic lactone, generated in this process

  （+）-apkukurodinone-1的不对称正式合成是通过一种途径实现的，其中氢键充当控制分子内Diether-Alder（IMDA）分子内Diels-Alder（IMDA）反应的π面选择性的立体化学控制元素。吡喃酮。在IMDA方法中，通过与烯酮羰基氧键合的分子内氢键，以高效方式传递烯键二烯亲烯体中带有α-碳的立构羟基的构型。在此过程中产生的三环内酯已成功转化为Danishefsky合成apkukurodinone-1的后期中间体。
• Protecting-Group-Free Total Synthesis of Aplykurodinone-1
  作者：Yu Tang、Ji-tian Liu、Ping Chen、Ming-can Lv、Zhen-zhen Wang、Yi-kun Huang

  DOI：10.1021/jo501684k

  日期：2014.12.5

  A concise, stereoselective, and protecting-group-free total synthesis of aplykurodinone-1 from Hajos–Parrish ketone was described. The synthetic approach features a sequence of aerobic allylic oxidation and elimination of alcohol 9. The key intermediate for this synthesis was formed by a stereoselective intramolecular radical cyclization.

  简明，立体选择性和无保护基的从Hajos–Parrish酮合成aplykurodinone-1。合成方法的特点是有氧烯丙基氧化和消除酒精9的顺序。该合成的关键中间体是通过立体选择性分子内自由基环化形成的。
• Total Synthesis of Aplykurodinone-1
  作者：Gang Liu、Guangjian Mei、Runwen Chen、Haina Yuan、Zhen Yang、Chuang-chuang Li

  DOI：10.1021/ol502220r

  日期：2014.9.5

  The concise total synthesis of aplykurodinone-1 with an unusual cis-fused hydrindane moiety has been accomplished without the need for any protecting group chemistry using a unique SmI2 mediated reductive cascade cyclization reaction and a direct cuprate mediated 1,4-addition. This work represents the first example of the use of a SmI2-mediated intramolecular cascade cyclization reaction between “halide

  使用独特的SmI 2介导的还原级联环化反应和直接的铜酸盐介导的1,4-加成，无需任何保护基团化学即可完成具有不寻常的顺式稠合的茚满环部分的aplykurodinone-1的简明全合成。这项工作代表在“卤化物，烯烃和醛”基团之间使用SmI 2介导的分子内级联环化反应的第一个例子。
• Formal Synthesis of (±)-Aplykurodinone-1 through a Hetero-Pauson–Khand Cycloaddition Approach
  作者：Cheng Tao、Jing Zhang、Xiaoming Chen、Huifei Wang、Yun Li、Bin Cheng、Hongbin Zhai

  DOI：10.1021/acs.orglett.7b00068

  日期：2017.3.3

  The tricyclic intermediate 2 has been synthesized in eight steps from known compound 6 in 20% overall yield. As such, this constitutes a highly efficient formal synthesis of (±)-aplykurodinone-1. This synthesis features a unique, one-pot, intramolecular hetero-Pauson-Khand reaction (h-PKR)/desilylation sequence to expeditiously construct the tricyclic framework, providing valuable insights for expanding

  三环中间体2已由已知化合物6分八步合成，总收率为20％。因此，这构成了（±）-apkukurodinone-1的高效形式合成。该合成具有独特的一锅分子内异Pauson-Khand反应（h -PKR）/去甲硅烷基化序列，可快速构建三环框架，为扩展h -PKR的范围和边界提供了宝贵的见识。
• Formal synthesis of degraded sterol (+)-aplykurodinone-1
  作者：Nishant Singh、Kiran Kumar Pulukuri、Tushar Kanti Chakraborty

  DOI：10.1016/j.tet.2015.05.026

  日期：2015.7

  The formal synthesis of aplykurodinone-1 is accomplished starting from a suitably functionalized bicyclic lactone having the requisite cis-fused ring junction with a quaternary chiral center that was assembled following a Cp2TiCl-mediated radical cyclization protocol. Our synthetic route further elaborates implementation of Grubbs ring closing metathesis (RCM), Eschenmoser-Claisen rearrangement and iodo-lactonization reactions for the synthesis of the final tricyclic precursor of the target molecule. (C) 2015 Elsevier Ltd. All rights reserved.