dihydro-ar-turmerone | 30666-87-6

• 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: dihydro-ar-turmerone
• 英文别名: 2-methyl-6-(p-tolyl)heptan-4-one；ar-Dihydroturmeron；2-methyl-6-(4-methylphenyl)heptan-4-one
• CAS: 30666-87-6
• 化学式: C₁₅H₂₂O
• 分子量: 218.339
• InChiKey: FWSUEHMNQCROMJ-UHFFFAOYSA-N

物化性质

• 沸点：
  301.2±11.0 °C(Predicted)
• 密度：
  0.925±0.06 g/cm3(Predicted)
• 保留指数：
  1597.5;1586;1591

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  dihydro-ar-turmerone 在 tin(II) chloride dihdyrate 、 dichloro[4,5-bis(diphenylphosphino)-9,9’-dimethylxanthene]palladium(II) 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 80.0 ℃ 、4.0 MPa 条件下， 反应 18.0h， 生成 3-Methyl-5-[2-(4-methylphenyl)propyl]-5-(2-methylpropyl)oxolan-2-one
  参考文献：
  名称：

  Selectivity controlled by ligand tuning in the palladium-catalysed cyclocarbonylation: Synthesis of new γ and δ lactones from a natural sesquiterpene

  摘要：

  The cyclocarbonylation of homoallylic alcohols, derived from alpha-atlantone, catalysed by [Pd(Cl-2)L-2]/SnCl2] system, afforded new gamma and delta lactones as the main products with high selectivities. The regiochemical control depends on the nature of phosphines involved. Catalysts based on monophosphines with large cone angles such as tricyclohexyl phosphine produce the six-membered ring lactones with selectivities up to 80%, while diphosphines with wide bite angle such as xantphos are found to favor the five-membered ring lactones with up to 99% selectivity. Monocrystals of the gamma and delta lactones suitable for X-ray diffraction analysis have been obtained and the stereochemistry of the lactones 5a,a' and 6 have been elucidated. This study is the first example of an attractive catalytic transformation of one single natural sesquiterpene easily available from bio-renewable resources to obtain either -gamma- or delta-lactones. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.02.010
• 作为产物：
  描述：

  异戊酸甲酯 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 生成 dihydro-ar-turmerone
  参考文献：
  名称：

  Electroorganic chemistry. 138. Electrochemically promoted cyclocoupling of 1,3-dienes or styrenes with aliphatic carboxylic esters

  摘要：

  The cathodic cyclocoupling of 1,3-dienes 1 with aliphatic esters 2 is promoted by a magnesium electrode and yields homologs of 3-cyclopentenol. Under similar reaction conditions, the coupling of styrenes with 2 affords 2-phenylcyclopropanol derivatives, and this coupling reaction has been successfully applied to the synthesis of ar-dihydroturmerone and curcumone.

  DOI：

  10.1021/jo00047a003

文献信息

• Ketone Synthesis by Direct, Orthogonal Chemoselective Hydroacylation of Alkenes with Amides: Use of Alkenes as Surrogates of Alkyl Carbanions
  作者：Hui Geng、Pei‐Qiang Huang

  DOI：10.1002/cjoc.201900252

  日期：2019.8

  and direct transformation of carboxamides are two exciting areas that have attracted considerable attention in recent years. We report herein that secondary amides, the least reactive derivatives of carbonyl compounds, upon activated with triflic anhydride, can serve as effective hydroacylating reagents in partner with alkenes to yield ketones at ambient temperature. The method was applied to the one‐step

  烯烃的直接官能化和羧酰胺的直接转化是近年来令人瞩目的两个令人兴奋的领域。我们在此报道，仲酰胺，即羰基化合物的反应性最低的衍生物，在用三氟甲磺酸酐活化后，可以与烯烃一起作为有效的氢酰化试剂，在环境温度下产生酮。该方法已用于外消旋二氢芳基羟色酮的一步合成。在这种方法中，烯烃用作有机金属试剂的替代物，从而可以进行正交的化学选择性反应。许多烯烃（如camp烯和降冰片烯）的现成性允许一步合成酮，而传统方法则需要几个步骤。
• Branched-Selective Intermolecular Ketone α-Alkylation with Unactivated Alkenes via an Enamide Directing Strategy
  作者：Dong Xing、Guangbin Dong

  DOI：10.1021/jacs.7b08581

  日期：2017.10.4

  We describe a strategy for intermolecular branched-selective α-alkylation of ketones using simple alkenes as the alkylating agents. Enamides derived from isoindolin-1-one provide an excellent directing template for catalytic activation of ketone α-positions. High branched selectivity is obtained for both aliphatic and aromatic alkenes using a cationic iridium catalyst. Preliminary mechanistic study

  我们描述了一种使用简单烯烃作为烷基化剂的酮的分子间支化选择性 α-烷基化策略。衍生自 isoindolin-1-one 的烯酰胺为酮 α 位的催化活化提供了极好的导向模板。使用阳离子铱催化剂可以为脂肪族和芳香族烯烃获得高支化选择性。初步机制研究有利于 Ir-C 迁移插入途径。
• Tf₂O/TTBP (2,4,6-Tri-<i>tert</i>-butylpyrimidine): An Alternative Amide Activation System for the Direct Transformations of Both Tertiary and Secondary Amides
  作者：Qian He、Jian-Liang Ye、Fang-Fang Xu、Hui Geng、Ting-Ting Chen、Hang Chen、Pei-Qiang Huang

  DOI：10.1021/acs.joc.1c01572

  日期：2021.12.3

  were generally obtained. In addition, Tf2O/TTBP combination was used to promote the condensation reactions of 2-(tert-butyldimethylsilyloxy)furan (TBSOF) with both tertiary and secondary amides, the one-pot reductive Bischler–Napieralski-type reaction of tertiary lactams, and Movassaghi and Hill’s modern version of the Bischler–Napieralski reaction. The value of the Tf2O/TTBP-based methodology was further

  研究了十种 Tf 2 O/TTBP 介导的酰胺转化反应。结果表明，与吡啶衍生物2,6-二叔丁基-4-甲基吡啶（DTBMP）和2-氟吡啶（2-F-Pyr.）相比，TTBP可以作为直接转化的替代酰胺活化体系。二级和三级酰胺。对于大多数调查的例子，通常获得更高或相当的产量。此外，Tf 2 O/TTBP组合用于促进2-(叔-丁基二甲基甲硅烷氧基）呋喃（TBSOF）与叔酰胺和仲酰胺，叔内酰胺的一锅还原比施勒-纳皮拉斯基反应，以及 Movassaghi 和希尔的现代版比施勒-纳皮拉斯基反应。几种天然产物的简明和高产合成进一步证明了基于Tf 2 O/TTBP 的方法的价值。
• The Regioselective Amino-exchange Reaction of β-Amino Conjugated Enones
  作者：Choji Kashima、Yasuhiro Yamamoto

  DOI：10.1246/bcsj.52.1735

  日期：1979.6

  By heating with various amines, the amino-exchange reaction of β-amino conjugated enones was regioselectively accomplished on β-carbon to give the corresponding β-amino conjugated enones. The resulting β-dialkylamino conjugated enones could then be used for the synthesis of β,β-disubstituted conjugated enones by treatment with Grignard reagents.

  通过与各种胺一起加热，β-氨基共轭烯酮的氨基交换反应可在β-碳上选择性地完成，从而得到相应的β-氨基共轭烯酮。得到的 β-二烷基氨基共轭烯酮可通过格氏试剂处理，用于合成 β,β-二取代共轭烯酮。
• A SHORT SYNTHESIS OF<i>ar</i>-TODOMATUIC ACID AND DIHYDRO-<i>ar</i>-TURMERONE BY THE HECK REACTION
  作者：S. B. Solabannavar、P. P. Wadgaonkar、U. V. Desai、R. B. Mane

  DOI：10.1080/00304940309355852

  日期：2003.8

  isolated from Himulayan Cedar wood by Bisarya and Sukh Dev.6 Crawford et ~ 1 . ~ have reported a three-step synthesis of 3b from limonene in 45% overall yield. We report here a two-step, efficient synthesis of 3a and 3b by a Heck reac t i~n .~*~ The Heck reaction* has been extended9 to allylic alcohols to yield aldehydes, ketones or aryl-substituted allylic alcohols depending on whether the alcohol is primary

  Sakai 和 Hirose 报道了从花旗松中分离出 ar-todomatuic 酸 (3a)。ar-Juvabione，ar-todomatuic acid (3, R=CO2CH3) 的甲酯，表现出与 juvabione 相似的保幼激素活性，2s3 作为第三代农药引起了相当大的关注！Mane 等 1 报道了 3a 的三步合成。~ 3 ~ 和 Krishna Rao 等人 1.5 从 3-苯基丁酸和苯乙烯基异丁基酮分别以 14% 和 10% 的收率。Bihydro-ar-turmerone (3b) 是由 Bisarya 和 Sukh Dev.6 Crawford 等人从喜马拉雅雪松木中分离出来的。~ 报道了从柠檬烯以 45% 的总产率三步合成 3b。我们在这里报告了通过 Heck 反应 3a 和 3b 的两步有效合成。~*~ Heck 反应*已扩展到烯丙醇以产生醛，酮或芳基取代的烯丙醇