(+/-)-(4aα,7α,7aα)-hexahydro-7-methylcyclopentapyran-3(1H)-one | 16802-11-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+/-)-(4aα,7α,7aα)-hexahydro-7-methylcyclopentapyran-3(1H)-one
• 英文别名: 7-methyl-1,3,4,4a,5,6,7,7a-octahydrocyclopenta[c]pyran-3-one；(±) 7-epi-boschnialactone；(4aR,7S,7aR)-7-methyl-4,4a,5,6,7,7a-hexahydro-1H-cyclopenta[c]pyran-3-one
• CAS: 16802-11-2；16802-12-3；16802-13-4；16802-14-5；17957-87-8；105181-38-2；131726-13-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: VGWJUWSHYRJZKH-XLPZGREQSA-N

物化性质

• 熔点：
  56-57 °C
• 沸点：
  265.2±8.0 °C(predicted)
• 密度：
  1.040±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-(4aα,7α,7aα)-hexahydro-7-methylcyclopentapyran-3(1H)-one 在 platinum(IV) oxide 、 氢气 、 sodium hydride 作用下， 以 甲醇 、 乙醇 、 二乙醇胺 、 mineral oil 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 24.0h， 生成 (4aa,7aa)-八氢-4b,7a-二甲基环戊并[c]吡喃-3-酮
  参考文献：
  名称：

  Cp 2 TiCl促进的自由基环化的应用：合成虹彩类单萜的统一策略

  摘要：

  一种简便的手性纯净形式的统一合成（+）-iridomyrmecin，（-）-isoiridomyrmecin，（+）-7- epi -boschnialactone，（+）- teucriumlactone和（-）-dolichodial的统一总合成方法结合了步骤经济性和简便性来描述可利用的（+）-β-香茅烯。亮点包括Ti（III）介导的还原性环氧开放环化反应，用于构建环烯醚酮内酯的核心环戊环[ c ]吡喃骨架，并且对新创建的桥头型立体中心具有完全的非对映选择性。随后的转化有利于短距离访问（+）-四氢内酯和（-）-二齿二元，并正式访问可能的其他虹彩。

  DOI：

  10.1021/acs.joc.8b00752
• 作为产物：
  描述：

  己二酸二乙酯 在 盐酸 、 sodium tetrahydroborate 、 二甲基硫 、 sodium ethanolate 、 potassium carbonate 、 对甲苯磺酸 、 臭氧 作用下， 以 甲醇 、 乙醚 、 苯 为溶剂， 反应 27.5h， 生成 (+/-)-(4aα,7α,7aα)-hexahydro-7-methylcyclopentapyran-3(1H)-one
  参考文献：
  名称：

  Cyclopentenyllithium additions to chiral aldehydes. Diastereofacial selectivity indicating the absence of a pronounced neighboring carboxylate anion effect

  摘要：

  The 1,2-addition of cyclopentenyllithium to a series of three five-membered aldehydo esters and their hemiacylals has been examined in order to assess the level and direction of facial selectivity surrounding nucleophilic attack at the aldehyde carbonyl and to clarify possible electronic and steric contributions stemming from neighboring functional groups. Neither methyl substitution of the acetic acid (ester) side chain nor the interchange of ester for carboxylate anion serve as important diastereocontrol elements. Instead, diastereofacial selectivity in these and related cyclic carboxaldehydes is governed by the inherent structural features of the ring system to which the functional group is attached. The convenient preparation of a complete subset of isomerically pure bicyclic lactones carrying five stereogenic centers is reported.

  DOI：

  10.1021/jo00012a013

文献信息

• Catalyst-Controlled Inverse-Electron-Demand Hetero-Diels−Alder Reactions in the Enantio- and Diastereoselective Synthesis of Iridoid Natural Products
  作者：David E. Chavez、Eric N. Jacobsen

  DOI：10.1021/ol034883l

  日期：2003.7.1

  [reaction: see text] Iridoid natural products 1-4 are accessed stereoselectively by means of tridentate (Schiff base)Cr(III)-catalyzed hetero-Diels-Alder reactions between ethyl vinyl ether and enantioenriched 5-methyl-1-cyclopentene-1-carboxaldehyde. An efficient route to the aldehyde from citronellal is afforded by the ring-closing metathesis reaction.

  [反应：参见正文]通过三齿（席夫碱）Cr（III）催化的乙基乙烯基醚与对映体富集的5-甲基-1-环戊烯-1之间的杂Diels-Alder反应，立体选择性地获得类虹彩天然产物1-4 -甲醛。闭环易位反应提供了从香茅醛到醛的有效途径。
• Syntheses of Several Cyclopentano-Monoterpene Lactones Using 1,3-Dioxin Vinylogous Ester.
  作者：Masashi OHBA、Tsuyoshi HANEISHI、Tozo FUJII

  DOI：10.1248/cpb.43.26

  日期：——

  Formal syntheses of (±)-boschnialactone (5) and three cyclopentano-monoterpene lactones [i.e., (±)-iridomyrmecin (6), (±)-isoiridomyrmecin (7), and (±)-allodolicholactone (8)] have been accomplished in the form of the syntheses of 2-(methoxymethyl)-3-methyl-2-cyclopenten-1-one (11) and (±)-(4aα, 7α, 7aα)-hexahydro-7-methylcyclopenta[c]pyran-3(1H)-one (19), respectively, starting from 6, 7-dihydrocyclopenta-1, 3-dioxin-5(4H)-one (2). A synthesis of (±)-isodehydroiridomyrmecin (9) has also been achieved through a route including direct substitution of the hydroxy group of 2-(tert-butyldimethylsilyloxymethyl)-3-methyl-2-cyclopenten-1-ol (22) with 1-(tert-butyldimethylsilyloxy)-1-methoxyethene (23) as a key step.

  已成功合成(±)-博希尼内酯（5）及三种环戊烯-单萜内酯，即(±)-蚁酸酯（6）、(±)-异蚁酸酯（7）和(±)-全罗松内酯（8），其合成过程分别利用了2-(甲氧基甲基)-3-甲基-2-环戊烯-1-酮（11）和(±)-(4aα, 7α, 7aα)-六氢-7-甲基环戊[c]吡喃-3(1H)-酮（19），起始材料为6, 7-二氢环戊-1, 3-二氧-5(4H)-酮（2）。同时，(±)-异脱氢蚁酸酯（9）的合成也已实现，合成路线的关键步骤为直接用1-(叔丁基二甲基氯硅氧基)-1-甲氧基乙烯（23）取代2-(叔丁基二甲基硅氧基甲基)-3-甲基-2-环戊烯-1-醇（22）中的羟基。
• Mechanism and applications of lithium amide-induced asymmetric rearrangements of 4-substituted and 4,4-disubstituted cyclopentene oxides to cyclopentenols
  作者：David M. Hodgson、Andrew R. Gibbs、Michael G. B. Drew

  DOI：10.1039/a907522d

  日期：——

  The preparation and lithium amide-induced rearrangements of 1,2-dideuterated 4-substituted cyclopentene oxides 11 and 19 are described, providing insight into the deprotonation mechanisms operating in such systems. Highly enantioselective syntheses of 4-substituted cis-4-hydroxymethylcyclopent-2-en-1-ols 32a–c are described. Also described are asymmetric syntheses of prostaglandin precursor 40 and (+)-iridomyrmecin (48) via highly enantioselective rearrangement of the epoxide 3 and subsequent Ireland–Claisen rearrangement.

  介绍了 1,2-二氚代 4-取代环戊烯氧化物 11 和 19 的制备和锂酰胺诱导的重排，为了解此类体系中的去质子化机制提供了见解。介绍了 4-取代顺式-4-羟甲基环戊-2-烯-1-醇 32a-c 的高对映选择性合成。还介绍了通过环氧化物 3 的高对映选择性重排和随后的爱尔兰-克莱森重排，不对称合成前列腺素前体 40 和 (+)-iridomyrmecin (48)。
• Iridoids : Stereospecific synthesis of functionalized cyclopentanoid intermediates via bicyclo[2.2.1]heptanones
  作者：P. Callant、P. Storme、E. Van der Eycken、M. Vandewalle

  DOI：10.1016/s0040-4039(00)94204-7

  日期：1983.1

  An efficient synthesis of functionalized trialkyl substituted cyclopentanoids is presented. Stereocontrol is secured by their formation from norbornane precusors. The strategy is illustrated by the total synthesis of (±)-boschnialactone (13), (±)-teucriumlactone C (14) and (±)-loganin (2).

  提出了功能化的三烷基取代的环戊烷的有效合成方法。通过降冰片烷前体的形成来确保立体控制。（±）-草内酯（13），（±）-te内酯C（14）和（±）-胶（2）的全合成说明了该策略。
• Baeyer–Villiger oxidation of bicycloheptanone to cyclopentapyranone: a novel synthesis of iridomyrmecin, isoiridomyrmecin, and boschnialactone
  作者：Tein-Fu Wang、Chi-Fu Yang

  DOI：10.1039/c39890001876

  日期：——

  Stereocontrolled syntheses of iridomyrmecin, isoiridomyrmecin, and boschnialactone are accomplished through a Baeyer–Villiger oxidation and either a cuprate coupling reaction or catalytic hydrogenation.

  iridomyrmecin，isoiridomyrmecin和boschnialactone的立体控制合成是通过Baeyer-Villiger氧化和铜酸盐偶联反应或催化氢化来完成的。