4-allyl-4-hydroxycyclohexanone | 915092-88-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-allyl-4-hydroxycyclohexanone
• 英文别名: 4-Hydroxy-4-prop-2-enylcyclohexan-1-one
• CAS: 915092-88-5
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: RJSXKKJOXGEJJP-UHFFFAOYSA-N

物化性质

• 沸点：
  242.8±33.0 °C(Predicted)
• 密度：
  1.045±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  4-allyl-4-hydroxycyclohexanone 在 氧气 、 palladium diacetate 、 4-甲基苯磺酸吡啶 、 臭氧 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 反应 125.0h， 生成
  参考文献：
  名称：

  Synthesis of a Functionalized Morphan Scaffold via a Palladium-Catalyzed Cycloalkenylation and Beckmann Rearrangement

  摘要：

  Functionalized 2-azabicyclo[3.3.1]nonan-3-ones, potential precursors to morphan, were assembled using a combination of a palladium-catalyzed cycloalkenylation and a Beckmann rearrangement.

  DOI：

  10.3987/com-16-s(s)74
• 作为产物：
  描述：

  8-烯丙基-1,4-二氧杂螺[4,5]癸烷-8-醇 在 盐酸 作用下， 以 水 为溶剂， 反应 24.0h， 以1.10 g的产率得到4-allyl-4-hydroxycyclohexanone
  参考文献：
  名称：

  New Bioorganic Reagents:  Evolved Cyclohexanone MonooxygenaseWhy Is It More Selective?

  摘要：

  Four mutants of the cyclohexanone monooxygenase (CHMO) evolved as catalysts for Baeyer-Villiger oxidation of 4-hydroxycyclohexanone were investigated as catalysts for a variety of 4-substituted and 4,4-disubstituted cyclohexanones. Several excellent catalytic matches (mutant/substrate) were identified. The most important, however, is the finding that, in a number of cases, a mutant with a single exchange, Phe432Ser, was shown to be as robust and more selective as a catalyst than the wild-type CHMO. All biotransformations were performed on a laboratory scale, allowing full characterization of the products. The absolute configurations of two products were established. A model suggesting a possible role of the 432 serine residue in enantioselectivity control is proposed.

  DOI：

  10.1021/jo061349t

文献信息

• Hydroxyl Group-Assisted Palladium-Catalyzed Lactonization of Homoallylic Alcohols
  作者：Liangbin Huang、Qian Wang、Wanqing Wu、Huanfeng Jiang

  DOI：10.1002/cctc.201300903

  日期：2014.2

  of α‐methylene‐γ‐lactones through the palladium(II)‐catalyzed lactonization of homoallylic alcohols with alkynamides has been reported. The hydroxyl group in the terminal olefins cooperates with the amide in alkynamides to promote the cyclization by suppressing the β‐H elimination. This process provides a route to construct naturally occurring biologically multifunctional α‐methylene‐γ‐lactones.

  据报道，通过钯（II）催化均烯丙基醇与炔酰胺的内酯化，可以方便高效地合成α-亚甲基-γ-内酯。末端烯烃中的羟基与炔基酰胺中的酰胺协同作用，通过抑制β-H的消除来促进环化。该过程提供了构建天然存在的生物多功能α-亚甲基-γ-内酯的途径。
• Baeyer-Villiger Oxidation and Oxidative Cascade Reactions with Aqueous Hydrogen Peroxide Catalyzed by Lipophilic Li[B(C6F5)4] and Ca[B(C6F5)4]2
  作者：Muhammet Uyanik、Daisuke Nakashima、Kazuaki Ishihara

  DOI：10.1002/anie.201204286

  日期：2012.9.3

  Efficient and selective: Two lipophilic catalysts were used for Baeyer–Villiger (BV) oxidations to give lactones in high yields (see scheme). Cascade reactions involving this BV oxidation were used to selectively obtain either unsaturated carboxylic acids or hydroxylactones in high yields from β‐silyl cyclohexanones.

  高效和选择性：两种亲脂性催化剂用于Baeyer-Villiger（BV）氧化，以高收率得到内酯（请参阅方案）。涉及这种BV氧化的级联反应用于从β-甲硅烷基环己酮中高收率选择性地获得不饱和羧酸或羟基内酯。
• METHOD FOR MANUFACTURING ESTER
  申请人：Ishihara Kazuaki

  公开号：US20130217898A1

  公开（公告）日：2013-08-22

  The present invention relates to a method for manufacturing an ester from a ketone or an aldehyde, which is a reactive substrate, by a Baeyer-Villiger oxidation reaction using hydrogen peroxide, and in this method, as a catalyst, M(BAr 4 ) n , which is a metal borate, is used (M represents an alkali metal or an alkaline earth metal; Ar represents an aryl; and n is the same number as the valence of M). For example, when cyclohexanone was used as the reactive substrate, and Sr[B(3,5-CF 3 C 6 H 3 ) 4 ] 2 was used as the catalyst, ε-caprolactone was obtained at an isolated yield of 82%.

  本发明涉及一种从酮或醛（作为反应底物）制造酯的方法，该方法通过使用过氧化氢进行巴耶-维利格氧化反应，在该方法中，作为催化剂使用了M(BAr4)n，该催化剂是一种金属硼酸盐（M代表碱金属或碱土金属；Ar代表芳基；n与M的化合价相同）。例如，当环己酮作为反应底物，Sr[B(3,5-CF3C6H3)4]2作为催化剂时，得到了ε-己内酯，其分离收率为82%。
• Oligomer-Opioid Agonist Conjugates
  申请人：Riggs-Sauthier Jennifer

  公开号：US20100048602A1

  公开（公告）日：2010-02-25

  The invention provides compounds that are chemically modified by covalent attachment of a water-soluble oligomer. A compound of the invention, when administered by any of a number of administration routes, exhibits characteristics that are different from those of the compound not attached to the water-soluble oligomer.

  该发明提供了通过共价连接水溶性寡聚体进行化学修饰的化合物。该发明的化合物在通过任何一种给药途径给予时，表现出与未连接水溶性寡聚体的化合物不同的特性。
• OLIGOMER-OPIOID AGONIST CONJUGATES
  申请人：RIGGS-SAUTHIER Jennifer

  公开号：US20120289548A1

  公开（公告）日：2012-11-15

  The invention provides compounds that are chemically modified by covalent attachment of a water-soluble oligomer. A compound of the invention, when administered by any of a number of administration routes, exhibits characteristics that are different from those of the compound not attached to the water-soluble oligomer.

  该发明提供了通过共价连接水溶性寡聚体进行化学修饰的化合物。 该发明的化合物在通过任何一种给药途径给予时，表现出与未连接水溶性寡聚体的化合物不同的特性。