(+)-6-hydroxycyclohexen-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-6-hydroxycyclohexen-2-one
• 英文别名: 6-Hydroxy-2-cyclohexen-1-one；6-hydroxycyclohex-2-en-1-one
• 化学式: C₆H₈O₂
• mdl: MFCD24393540
• 分子量: 112.128
• InChiKey: SQTOTUFHUQHDQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-6-hydroxycyclohexen-2-one 在 正丁基锂 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 17.25h， 生成
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r
• 作为产物：
  描述：

  1,3-环己二烯 在 过氧乙酸 、 osmium (III) chloride 作用下， 以 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 3.0h， 以52%的产率得到(+)-6-hydroxycyclohexen-2-one
  参考文献：
  名称：

  Osmium-Catalyzed Oxidative Transformation of Alkenes to α-Ketols with Peracetic Acid

  摘要：

  OsCl3催化的烯烃在室温下与过乙酸的氧化反应产生相应的α-酮醇，这是合成生物活性化合物的重要构建单元。

  DOI：

  10.1246/cl.1993.1767

文献信息

• [EN] COMPOSITIONS AND METHODS FOR THE PREPARATION OF 4-OXY-2-CYCLOHEXENONE AND 6-OXY-2-CYCLOHEXENONE COMPOUNDS<br/>[FR] COMPOSITIONS ET PROCÉDÉS POUR LA PRÉPARATION DE COMPOSÉS 4-OXY-2-CYCLOHEXÉNONE ET 6-OXY-2-CYCLOHEXÉNONE
  申请人：UNIV NAT TAIWAN

  公开号：WO2016011130A1

  公开（公告）日：2016-01-21

  The present invention relates to a new synthetic route to 4-oxy-2-cyclohexenone and 6-oxy-2- cyclohexenone compounds useful for treatment of cancers and/or diseases, and the intermediates thereto. Examples of these cyclohexenone compounds include, but not limited to, A. cinnamomea active medicinal substances such as antroquinonol, antroquinonol B, antroquinonol C, and antroquinonol D. The intermediates include the compounds of formulae (I), (II) and (III), and the cyclohexenone compounds have the structures of formulae (IV), (V), (VI) and (VII).

  本发明涉及一种用于治疗癌症和/或疾病的新的合成路线，用于制备4-氧基-2-环己烯酮和6-氧基-2-环己烯酮化合物，以及这些化合物的中间体。这些环己烯酮化合物的示例包括但不限于A.桂枝活性药物成分，如antroquinonol，antroquinonol B，antroquinonol C和antroquinonol D。这些中间体包括式(I)、(II)和(III)的化合物，环己烯酮化合物具有式(IV)、(V)、(VI)和(VII)的结构。
• Total synthesis of (+)-blennolide C and (+)-gonytolide C via spirochromanone
  作者：Kanna Adachi、Sho Hasegawa、Kazuaki Katakawa、Takuya Kumamoto

  DOI：10.1016/j.tetlet.2017.10.038

  日期：2017.11

  We report the asymmetric total synthesis of (+)-blennolide C and (+)-gonytolide C isolated from endophytic fungi. The synthesis involved construction of a spirochromanone with a chiral quaternary carbon by the aldol reaction of o-hydroxyacetophenones and optically active α-oxygenated cyclohexenone, followed by cyclization under acidic conditions. Oxidative cleavage of the alkene moiety of the spirochromanone

  我们报告从内生真菌中分离出来的（+）-布兰诺利德C和（+）-gonytolide C的不对称总合成。一个spirochromanone的合成涉及的结构与通过醛醇缩合反应手性季碳ö -hydroxyacetophenones和光学活性的α-氧化环己烯酮，接着在酸性条件下环化。螺并苯并二氢吡喃酮的烯烃部分的氧化裂解提供了苯并二氢吡喃酮二酯。通过用路易斯酸处理二酯，通过去保护二酯的氧官能度并同时进行Dieckmann缩合反应，实现了（+）-亚油酸内酯C的第一个全合成。还可以通过由脱保护的二酯形成内酯来实现（+）-去甲内酯C的全合成。
• Epoxidation of Olefinic Compounds with Combined Use of Molecular Oxygen and Propionaldehyde Diethyl Acetal Catalyzed by Cobalt(II) Complex. Efficient Method for the Preparation of Acid-sensitive Epoxides
  作者：Kiyotaka Yorozu、Toshihiro Takai、Tohru Yamada、Teruaki Mukaiyama

  DOI：10.1246/cl.1993.1579

  日期：1993.9

  Synthesis of acid-sensitive epoxides such as epoxide of bishomoallyl alcohol or chromene oxide was achieved by the epoxidation of corresponding olefins with combined use of molecular oxygen and propionaldehyde diethyl acetal catalyzed by cobalt(II) complex. Various silyl enol ethers and silyl ketene acetals, acid-sensitive compounds, were also smoothly monooxygenated into the corresponding α-hydroxy

  通过在钴（II）配合物的催化下，通过分子氧和丙醛二乙缩醛的组合使用相应烯烃的环氧化反应来合成酸敏感的环氧化物，例如双单烯丙醇的环氧化物或氧化色烯。各种甲硅烷基烯醇醚和甲硅烷基乙烯酮缩醛，酸敏感化合物，也顺利地单氧化成相应的α-羟基羰基化合物。
• A Novel Method for the Preparation of Acid-Sensitive Epoxides from Olefins with the Combined Use of Molecular Oxygen and Aldoacetal Catalyzed by a Cobalt(II) Complex
  作者：Kiyotaka Yorozu、Toshihiro Takai、Tohru Yamada、Teruaki Mukaiyama

  DOI：10.1246/bcsj.67.2195

  日期：1994.8

  An efficient synthesis of acid-sensitive epoxides, such as chromene oxide or epoxide of γ,δ-unsaturated alcohol, was successfully achieved by the oxygenation of corresponding olefins with the combined use of an atmospheric pressure of molecular oxygen and aldoacetal catalyzed by a cobalt(II) complex coordinated with the 1,3-diketone ligand. The reactions proceeded under mild and neutral conditions

  通过在常压下分子氧和醛缩醛的协同作用，将相应的烯烃氧化，并在钴催化下，成功地合成了酸敏感环氧化物，如色烯氧化物或γ,δ-不饱和醇的环氧化物（ II) 与 1,3-二酮配体配位的复合物。反应在温和且中性的条件下进行，并以良好的收率获得所需的环氧化物。在本反应条件下，既没有观察到过氧化也没有观察到形成的环氧化物分解。此外，各种甲硅烷基烯醇醚和甲硅烷基烯酮缩醛，酸敏感化合物，也分别顺利地单氧化成相应的 α-羟基酮和 α-羟基羧酸酯。
• THE OXYGENATION OF α-ISOPHORONE AND ITS SILYL ENOL ETHER WITH<i>t</i>-BuOOH IN THE PRESENCE OF METAL CATALYSTS
  作者：Takahiro Hosokawa、Shiro Inui、Shun-Ichi Murahashi

  DOI：10.1246/cl.1983.1081

  日期：1983.7.5

  Treatment of α-isophorone (1) with t-BuOOH in the presence of palladium(II) or copper(I) catalyst gives ketoisophorone (2) selectively. A similar treatment of silyl enol ether 7 derived from 1 affords 6-hydroxylisophorone 8.

  用t-BuOOH处理α-异佛尔酮(1)在铂(II)或铜(I)催化剂的存在下，可以选择性地得到酮异佛尔酮(2)。对由1衍生的硅醇醚7进行类似处理，得到6-羟基异佛尔酮8。