(1S*,3aS*,4R*,6aR*)-1,4-dimethyl-3,3a,4,5,6,6a-hexahydro-2(1H)-pentalenone | 57764-39-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S*,3aS*,4R*,6aR*)-1,4-dimethyl-3,3a,4,5,6,6a-hexahydro-2(1H)-pentalenone
• 英文别名: (1R,3aR,4S,6aS)-1,4-dimethyl-3,3a,4,5,6,6a-hexahydro-1H-pentalen-2-one
• CAS: 57764-39-3；63700-72-1；79465-30-8；114419-92-0；130008-74-1；142129-21-3；142129-22-4
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: XRCQDEUXKSKYGE-JQCXWYLXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S*,3aS*,4R*,6aR*)-1,4-dimethyl-3,3a,4,5,6,6a-hexahydro-2(1H)-pentalenone 在 sodium tetrahydroborate 作用下， 生成 (1R,2S,3aR,4S,6aS)-1,4-Dimethyl-octahydro-pentalen-2-ol
  参考文献：
  名称：

  Carbon-13 chemical shifts in bicyclo[3.3.0]octanes

  摘要：

  DOI：

  10.1021/jo00444a018
• 作为产物：
  描述：

  5-甲基四氢吡喃-2-酮 在 偶氮二异丁腈 、 四溴化碳 、 水 、 三苯基膦 、 苯亚磺酸 作用下， 以 乙腈 为溶剂， 生成 (1S*,3aS*,4R*,6aR*)-1,4-dimethyl-3,3a,4,5,6,6a-hexahydro-2(1H)-pentalenone
  参考文献：
  名称：

  立体选择性串联自由基环化：异艾霉素的合成

  摘要：

  溴化物的串联自由基环化反应（8b）导致了双环酮（13），这是异艾霉素的合成中间体（14），表明如果适当地取代前体，可以实现无环前体的高度立体选择性串联环化反应。

  DOI：

  10.1016/0040-4039(90)80106-v

文献信息

• Total Synthesis of (+)-Epoxydictymene. Application of Alkoxy-Directed Cyclization to Diterpenoid Construction
  作者：Leo A. Paquette、Li-Qiang Sun、Dirk Friedrich、Paul B. Savage

  DOI：10.1021/ja971526v

  日期：1997.9.1

  stereoselectively. Some functional group manipulation led to 57 and 58, both of which underwent efficient cyclization to deliver the complete framework of the target molecule when irradiated with visible light in cyclohexane solution containing iodosobenzene diacetate and iodine. The generality of this key reaction, which efficiently constructs the strained oxabicyclo[3.3.0]octane subunit of 1, is dem...

  报道了 (+)-epoxydictymene (1) 的对映选择性合成。对映体纯醛酯 5 与 (S)-3-异丙基环戊烯基锂的缩合选择性地进行以提供 13。一旦该内酯被 Tebbe 试剂亚甲基化，新形成的烯丙基乙烯基醚在三异丁基铝的催化下被诱导进入克莱森重排。所得二环五环辛烯酮衍生物的连续硼氢化-氧化之后是羰基官能团的角甲基化和脱氧。在 C-11 处差向异构化后，α-羟基被区域和立体选择性地引入。一些官能团操纵导致了 57 和 58，当在含有碘代苯二乙酸酯和碘的环己烷溶液中用可见光照射时，两者都经历了有效的环化以提供目标分子的完整骨架。这个关键反应的普遍性，它有效地构建了 1 的应变氧杂双环 [3.3.0] 辛烷亚基，是...
• Iridoids : Novel total synthesis of (±)- isoiridomyrmecin and of (±)-verbenalol
  作者：Paul Callant、Raymond Ongena、Maurits Vandewalle

  DOI：10.1016/s0040-4020(01)97962-1

  日期：1981.1

  A novel synthesis of the iridoids (±)-isoiridomyrmecin 1 and (±verbenalol 2 is described starting from the tricyclo |3.3.0.02,8|octan-3-one 3 using cis fused bicyclo |3.3.0|octenes as intermediates. The heterocyclic ring of the iridoids was formed in the final stages of the syntheses.

  从顺式稠合的双环| 3.3.0 |辛烯为中间体的三环| 3.3.0.0 2,8 | octan -3-one 3开始，描述了虹彩化合物（±）-异虹鳟霉素1和（±邻苯二酚2）的新颖合成。在合成的最后阶段中形成了虹彩化合物的杂环。
• New Asymmetric Syntheses of (-)-Isoiridomyrmecn and (+)-Loganin Aglucon 6-Acetate Utilizing C2-Symmetric Dimethyl 3,7-Dihydroxy-cis-bicyclo[3.3.0]octa-2,6-diene-2,6-dicarboxylate.
  作者：Manabu NODE、Mamoru ARAKI、Hiroaki TANAKA、Daisaku NAKAMURA、Takehisa INOUE、Kiyoharu NISHIDE

  DOI：10.1248/cpb.46.736

  日期：——

  The first asymmetric synthesis of (-)-isoiridomyrmecin and formal synthesis of (-)-loganin were done using chiral C2-symmetric building block dimethyl 3, 7-dihydroxy-cis-bicyclo[3.3.0]octa-2, 6-diene-2, 6-dicarboxylate (2) which was prepared by the lipase-catalyzed asymmetric demethoxy-carbonylation of tetramethyl 3, 7-dioxo-cis-bicyclo-[3.3.0]octane-2, 4, 6, 8-tetracarboxyrate (1).

  (-)-异伊里多霉素的首次不对称合成和(-)-洛根素的首次全合成均使用手性C2对称结构单元3,7-二羟基-顺式-双环[3.3.0]辛烷-2,6-二烯-2,6-二羧酸二甲酯（2）进行，该结构单元由四甲基3,7-二氧代-顺式-双环-[3.3.0]辛烷-2,4,6,8-四羧酸（1）经脂肪酶催化不对称脱甲氧基羰基化反应制备而成。
• Cyclopentenyllithium additions to chiral aldehydes. Diastereofacial selectivity indicating the absence of a pronounced neighboring carboxylate anion effect
  作者：Dirk Friedrich、Leo A. Paquette

  DOI：10.1021/jo00012a013

  日期：1991.6

  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.
• Diastereoselective zirconocene-promoted bicyclization-carbonylation of allylically methyl-substituted enynes. Synthesis of (+)-iridomyrmecin
  作者：Gilbert Agnel、Zbyslaw Owczarczyk、Ei-ichi Negishi

  DOI：10.1016/s0040-4039(00)91669-1

  日期：1992.3

  Allylically methyl-substituted 1,6-heptenynes, such as 3-methyl-1,6-octenyne, can be diastereoselectively converted to the corresponding bicyclic ketones, such as (5R,6S)-2,6-dimethylbicyclo[3.3.0]oct-1-en-3-one readily convertible to (+)-iridomyrmecin, the observed diastereomeric excesses of the bicyclization reaction being > 90%.