(+)-tetrahydronootkatone | 20489-54-7

• 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: (+)-tetrahydronootkatone
• 英文别名: Tetrahydronootkatone；(4R,4aS,6R,8aS)-4,4a-dimethyl-6-propan-2-yl-1,3,4,5,6,7,8,8a-octahydronaphthalen-2-one
• CAS: 20489-54-7
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: DDJJLKQSWUBTKH-CXTNEJHOSA-N

物化性质

• 沸点：
  292.2±8.0 °C(Predicted)
• 密度：
  0.919±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  (+)-tetrahydronootkatone 在 溴 作用下， 以 溶剂黄146 为溶剂， 反应 1.0h， 以32.6%的产率得到(1S,3R,4S,4aS,6R,8aR)-1,3-dibromo-6-isopropyl-4,4a-dimethyl-1,2,3,4,56,7,8-octahydronaphthalen-2-one
  参考文献：
  名称：

  The sesquiterpenoid nootkatone and the absolute configuration of a dibromo derivative

  摘要：

  Nootkatone, or (4R, 4aS, 6R)- 4,4a, 5,6,7,8- hexahydro-4,4a- dimethyl-6-( 1-methylethenyl) naphthalen-2(3H)-one, C15H22O, a sesquiterpene with strong repellent properties against Formosan subterranean termites and other insects, has the valencene skeleton. The dibromo derivative ( 1S, 3R, 4S, 4aS,6R, 8aR)- 1,3-dibromo-6-isopropyl-4,4a- dimethyl-1,2,3,4,5,6,7,8- octahydronaphthalen-2-one, C15H24Br2O, has two independent molecules in the asymmetric unit, which differ in the rotation of the isopropyl group with respect to the main skeleton. The C-Br distances are in the range 1.950 (4) - 1.960 (4) Angstrom. Both independent molecules form zigzag chains, with very short intermolecular carbonyl - carbonyl interactions, having the perpendicular motif and O...C distances of 2.886 (6) and 2.898 (6) Angstrom. These chains are flanked by intermolecular Br...Br interactions of distances in the range 4.067 (1) - 4.218 (1) Angstrom. The absolute configuration of the dibromo derivative was determined, from which that of nootkatone was inferred.

  DOI：

  10.1107/s010827010300684x
• 作为产物：
  描述：

  (+)-香柏酮 在 5% Pd(II)/C(eggshell) 、 氢气 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 (+)-tetrahydronootkatone
  参考文献：
  名称：

  （+）-Nootkatone，Tetrahydronootkatone和衍生物的高效，经济的不对称合成

  摘要：

  通过组合立体选择性格氏试剂/阴离子氧-应付（AOC）反应，已经建立了对映体纯的（+）-Nootkatone及其衍生物的简便途径。

  DOI：

  10.1021/ol8023709

文献信息

• Deacylative transformations of ketones via aromatization-promoted C–C bond activation
  作者：Yan Xu、Xiaotian Qi、Pengfei Zheng、Carlo C. Berti、Peng Liu、Guangbin Dong

  DOI：10.1038/s41586-019-0926-8

  日期：2019.3

  3-dienes. Specifically, the acyl group is removed from the ketone and transformed to a pyrazole, and the resulting alkyl fragment undergoes various transformations. These include the deacetylation of methyl ketones, carbenoid-free formal homologation of aliphatic linear ketones and deconstructive pyrazole synthesis from cyclic ketones. Given that ketones are prevalent in feedstock chemicals, natural products

  碳-氢（C-H）键和碳-碳（C-C）键是有机物的主要成分。C-H 功能化技术的最新进展极大地扩展了我们的有机合成工具箱。相比之下，能够编辑分子骨架的 C-C 激活方法仍然有限2-7。已经提出了几种催化 C-C 活化的方法，特别是使用酮底物，通常通过使用环应变释放作为热力学驱动力 4,6 或引导基团 5,7 来控制反应结果来促进这些方法。虽然有效，但这些策略需要包含高度应变的酮或预安装的导向基团的底物，或者仅限于更专业的底物类别 5。在这里，我们报告了由原位形成的前芳香族中间体的芳构化驱动的一般 C-C 活化模式。该反应适用于各种酮底物，由铱/膦组合催化，并由肼试剂和 1,3-二烯促进。具体而言，将酰基从酮中除去并转化为吡唑，并且所得烷基片段经历各种转化。这些包括甲基酮的脱乙酰化、脂肪族线性酮的无类卡宾正式同系化和从环酮中解构吡唑合成。鉴于酮在原料化学品、天然产品和药物中很普遍，这些转化可以
• Structure and Absolute Configuration of Kusunol
  作者：HIROSHI HIKINO、NORIO SUZUKI、TSUNEMATSU TAKEMOTO

  DOI：10.1248/cpb.16.832

  日期：——

  A new sesquiterpenic alcohol, kusunol, has been isolated from camphor blue oil, the high boiling fraction of the essential oil of camphor tree, Cinnamomum camphora (Lauraceae). The carbon skeleton and the positions of the double bond and the tertiary hydroxyl group have been deduced from the chemical and physico-chemical studies, which, together with its transformation to α-vetivone and nootkatone, have further permitted the allocation of the absolute stereostructure I to this sesquiterpenoid.

  一种新的倍半萜醇——库孙醇，从樟树（Lauraceae）的高沸点精油分馏樟脑蓝油中分离得到。通过化学和物理化学研究，推导出了其碳骨架、双键和三级羟基的位置，并且通过其转化为α-香根草酮和努特卡酮，进一步确定了该倍半萜的绝对立体结构I。
• An Efficient and Economic Asymmetric Synthesis of (+)-Nootkatone, Tetrahydronootkatone, and Derivatives
  作者：Anne M. Sauer、William E. Crowe、Gregg Henderson、Roger A. Laine

  DOI：10.1021/ol8023709

  日期：2009.8.20

  A facile route to enantiomerically pure (+)-nootkatone and derivatives has been established through conjunctive stereoselective Grignard/anionic oxy-Cope (AOC) reactions.

  通过组合立体选择性格氏试剂/阴离子氧-应付（AOC）反应，已经建立了对映体纯的（+）-Nootkatone及其衍生物的简便途径。
• Hydrogenation Selectivity of the Bicyclo[4.4.0]decane Ring System of Valencanes
  作者：Roger Laine、Anne Sauer、William Crowe、Gregg Henderson

  DOI：10.1055/s-0029-1219206

  日期：2010.2

  To test the selectivity of sterically hindered systems, (+)-nootkatone and derivatives were subjected to a wide variety of hydrogenation methodologies. The steric impact of the C-4 methyl substituent seems to be responsible for the inability of the system to adopt the cis-fused structure.

  为了测试空间位阻系统的选择性，对 (+)-nootkatone 和衍生物进行了多种氢化方法。C-4 甲基取代基的空间影响似乎是系统无法采用顺式融合结构的原因。
• Cobalt‐Catalyzed Cross‐Coupling of Functionalized Alkylzinc Reagents with (Hetero)Aryl Halides
  作者：Ferdinand H. Lutter、Lucie Grokenberger、Philipp Spieß、Jeffrey M. Hammann、Konstantin Karaghiosoff、Paul Knochel

  DOI：10.1002/anie.201914490

  日期：2020.3.27

  A combination of 10 % CoCl2 and 20 % 2,2'-bipyridine ligands enables cross-coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3- and 1,4-substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with

  10％CoCl2和20％2,2'-联吡啶配体的组合可实现官能化的伯烷基锌试剂和仲烷基锌试剂与各种（杂）芳基卤化物的交叉偶联。与1，3-和1，4-取代的环烷基锌试剂的偶联进行非对映选择性，导致官能化的杂环具有高达98：2的高非对映选择性。此外，炔基溴化物与伯和仲烷基锌试剂反应，提供烷基化的炔烃。