1-[(1R,5S)-6,6-二甲基双环[3.1.1]庚-2-烯-2-基]乙酮 | 228113-75-5

• 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
• 中文名称: 1-[(1R,5S)-6,6-二甲基双环[3.1.1]庚-2-烯-2-基]乙酮
• 英文名称: 1-{(1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl}ethanone
• 英文别名: 10-methylmyrtenone；1-((1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethan-1-one；Myrtenon；Ethanone, 1-[(1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl]-(9CI)；1-[(1R,5S)-6,6-dimethyl-2-bicyclo[3.1.1]hept-2-enyl]ethanone
• CAS: 228113-75-5
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: KVEJFJCLGGIDJP-WPRPVWTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  1-[(1R,5S)-6,6-二甲基双环[3.1.1]庚-2-烯-2-基]乙酮 在 platinum(IV) oxide 氢气 、 sodium ethanolate 作用下， 以 乙醇 、 苯 为溶剂， 生成 (+)-1-<(1S,2S)-6,6-dimethylbicyclo<3.1.1>hept-2-yl>ethanone
  参考文献：
  名称：

  Bessiere-Chretien,Y.; El Gaied,M.M., Bulletin de la Societe Chimique de France, 1971, p. 2189 - 2194

  摘要：

  DOI：
• 作为产物：
  描述：

  (-)-桃金娘烯醇 在 正溴丁烷 、 N-氯代丁二酰亚胺 、 magnesium 、 叔丁醇 作用下， 反应 13.25h， 生成 1-[(1R,5S)-6,6-二甲基双环[3.1.1]庚-2-烯-2-基]乙酮
  参考文献：
  名称：

  A Facile Synthesis of Aldehyde and Ketone via Senochemical Barbier Reaction and Oxidation

  摘要：

  AbstractMethyl ketone is prepared by a sonochemical Barbier reaction of methyl iodide, magnesium powder and aldehyde in Benzene/THF (9/1) solvent in a commercial ultrasonic cleaning bath (39 kHz), followed by the addition of N‐chlorosuccinimide (NCS) as an oxidizing agent.

  DOI：

  10.1002/jccs.199700010

文献信息

• Spiro[1,2]oxaphosphetanes of Nonstabilized and Semistabilized Phosphorus Ylide Derivatives: Synthesis and Kinetic and Computational Study of Their Thermolysis
  作者：Jesús García López、Pablo M. Sansores Peraza、María José Iglesias、Laura Roces、Santiago García-Granda、Fernando López Ortiz

  DOI：10.1021/acs.joc.0c01270

  日期：2020.11.20

  example of an isolated oxaphosphetane having a phenyl substituent at C3 of the ring. Kinetic studies of their thermal decomposition showed that the process takes place irreversibly through a polar transition state (ρ = −0.22) under the influence of electronic, [1,2], [1,3] steric, and solvent effects, with C3/P-[1,2] interactions as the largest contribution to ΔG⧧ of olefination. Inversion of the phosphorus

  通过稳定的一系列三和四取代的螺- oxaphosphetanes的邻-苯甲酰胺（Ò BA）和ñ -甲基邻-苯甲酰胺（M ö BA）配位体已经由C的反应，合成α，C邻-dilithiated磷腈与醛和酮。它们包括对映体纯产物和在环的C 3处具有苯基取代基的分离的氧杂膦烷的第一个实例。对它们的热分解的动力学研究表明，在电子，[1,2]，[1,3]空间和溶剂效应的影响下，该过程通过极性过渡态（ρ= -0.22）不可逆地发生，C3 / P- [1,2]相互作用是对Δ的最大贡献ģ ⧧烯的。在许多情况下已经观察到通过立体突变使磷构型反转。DFT计算表明，o BA衍生物通过分离的（N，O）（Ph，C 6 H 4，C）氧代磷杂环戊烷（通道A）烯化，而M o BA化合物则通过异构体（C 6 H 4，O）分解得更快由涉及M B2的P-立体突变形成的（C，N，Ph）排列机制（渠道B）。P-异构化的能垒低于烯化的
• Diastereoselective Synthesis of Five- and Seven-Membered Rings by [2+2+1], [3+2], [3+2+2], and [4+3] Carbocyclization Reactions of β-Substituted (Alkenyl)(methoxy)carbene Complexes with Methyl Ketone Lithium Enolates
  作者：José Barluenga、Jorge Alonso、Francisco J. Fañanás

  DOI：10.1002/chem.200500164

  日期：2005.8.19

  derived from a formal [2+2+1] carbocyclization reaction. However, the lithium enolates of acetone and tungsten complexes furnish formal [3+2+2] carbocyclization products. In the case of alkynyl methyl ketone lithium enolates, competitive formal [2+2+1] and [3+2] carbocyclization reactions occur and 1,3-cyclopentanediol and 3-cyclopentenol derivatives are formed. Conversely, alkenyl methyl ketone lithium enolates

  β-取代的烯基卡宾配合物与甲基酮烯醇锂反应，生成不同的碳环化产物，具体取决于烯醇锂的结构，卡宾配合物的金属以及反应介质。因此，芳基和烷基甲基酮烯醇锂与乙醚中的β-取代的烯基铬和钨卡宾络合物的反应提供了由正式的[2 + 2 + 1]碳环化反应衍生的1,3-环戊二醇衍生物。但是，丙酮和钨配合物的烯醇锂提供正式的[3 + 2 + 2]碳环化产物。在炔基甲基酮烯醇锂的情况下，发生竞争性形式的[2 + 2 + 1]和[3 + 2]碳环化反应，并形成1,3-环戊二醇和3-环戊烯醇衍生物。反过来，烯基甲基酮烯醇锂在相同反应条件下与烯基碳烯配合物反应，通过正式的[4 + 3]碳环化反应形成2-环庚烯酮衍生物。最后，当反应在配位介质存在下进行时，观察到的[3 + 2]碳环化模式与所使用的甲基酮烯醇锂的性质无关。
• Synthesis of α-oxygenated β,γ-unsaturated ketones by a catalytic rearrangement strategy
  作者：Luisa Lempenauer、Aline Soupart、Elisabet Duñach、Gilles Lemière

  DOI：10.1039/c8ob01559g

  日期：——

  A straightforward two-step entry to α-oxgenated β,γ-unsaturated ketones from readily available α,β-unsaturated ketones is disclosed. It was found that bis(allylic) alcohols undergo a skeletal rearrangement in the presence of 1 mol% of cheap and non-corrosive p-toluenesulfonic acid. Computational studies were conducted to support the mechanism and to rationalise the influence of the catalyst acidity

  公开了从容易获得的α，β-不饱和酮直接进入α-加氧的β，γ-不饱和酮的两步法。发现双（烯丙基）醇在1mol％的廉价且无腐蚀性的对甲苯磺酸的存在下发生骨架重排。进行了计算研究以支持该机理并合理化催化剂酸度对产物选择性的影响。
• New 2-acyl-1,3-dioxane derivatives from (1R)-(−)-myrtenal: stereochemical effect on their relative ability as chiral auxiliaries
  作者：Elvia Becerra-Martínez、Pedro Velázquez-Ponce、Miguel A. Sánchez-Aguilar、Alfredo Rodríguez-Hosteguín、Pedro Joseph-Nathan、Joaquín Tamariz、L. Gerardo Zepeda

  DOI：10.1016/j.tetasy.2007.10.047

  日期：2007.11

  Four 3,10-pinanediol derivatives 1a-d, prepared in 50-72% global yields from (IR)-(-)-myrtenal 2, were treated with (RO)(2)CHCOR3 (R-3 = CH3, Ph) to afford 2-acyl-1,3-dioxanes 3a-f. The latter were submitted to nucleophilic additions using several Grignard reagents to mainly afford carbinols generated by re diastereofacial attack (85-99% yield, >= 88:12 dr). The lowest diastereoselectivity was observed when PhLi or hydrides were used as nucleophiles. Only an equatorial substituent at C-3 modifies the diastereoselectivity of the nucleophilic additions. (c) 2007 Elsevier Ltd. All rights reserved.
• Angermund, Klaus; Eckerle, Anette; Lutz, Frank, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1995, vol. 50, # 3, p. 488 - 502
  作者：Angermund, Klaus、Eckerle, Anette、Lutz, Frank

  DOI：——

  日期：——