(-)-ambrox | 312700-06-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (-)-ambrox
• 英文别名: (-)-ambroxide；ambrofix；Ambroxide；(3aR,9aS,9bR)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran
• CAS: 312700-06-4
• 化学式: C₁₆H₂₈O
• 分子量: 236.398
• InChiKey: YPZUZOLGGMJZJO-BHUMPYGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-ambrox 在 Δ-[Fe(CF3SO3)2((R,R,R)-MCPP)] 、 双氧水 、 溶剂黄146 、 盐酸 作用下， 以 乙腈 、 水 为溶剂， 反应 4.0h， 以70%的产率得到(+)-sclareolide
  参考文献：
  名称：

  Regioselective Oxidation of Nonactivated Alkyl C–H Groups Using Highly Structured Non-Heme Iron Catalysts

  摘要：

  Selective oxidation of alkyl C-H groups constitutes one of the highest challenges in organic synthesis. In this work, we show that mononuclear iron coordination complexes Lambda-[Fe(CF3SO3)(2)((S,S,R)-MCPP)] (Lambda-1P), Delta-[Fe(CF3SO3)(2)((R,R,R)-MCPP)] (Delta-1P), Lambda-[Fe(CF3SO3)(2)((S,S,R)-BPBPP)] (Lambda-2P), and Delta-[Fe(CF3SO3)(2)((R,R,R)-BPBPP)] (Delta-2P) catalyze the fast, efficient, and selective oxidation of nonactivated alkyl C-H groups employing H2O2 as terminal oxidant. These complexes are based on tetradentate N-based ligands and contain iron centers embedded in highly structured coordination sites defined by two bulky 4,5-pinenopyridine donor ligands, a chiral diamine ligand backbone, and chirality at the metal (Lambda or Delta). X-ray diffraction analysis shows that in Lambda-1P and Lambda-2P the pinene rings create cavity-like structures that isolate the iron site. The efficiency and regioselectivity in catalytic C-H oxidation reactions of these structurally rich complexes has been compared with those of Lambda-[Fe(CF3SO3)(2)((S,S)-MCP)] (Lambda-1), Lambda-[Fe(CF3SO3)(2)((S,S)-BPBP)] (Lambda-2), Delta-[Fe(CF3SO3)(2)((R,R)-BPBP)] (Delta-2), Lambda-[Fe(CH3CN)(2)((S,S)-BPBP)] (SbF6)(2) (Lambda-2SbF(6)), and Delta-[Fe(CH3CN)(2)((R,R)-BPBP)](SbF6)(2) (Delta-2SbF(6)), which lack the steric bulk introduced by the pinene rings. Cavity-containing complexes Lambda-1P and Lambda-2P exhibit enhanced activity in comparison with Delta-1P, Delta-2P, Lambda-1, Lambda-2, and Lambda-2SbF(6). The regioselectivity exhibited by catalysts Lambda-1P, Lambda-2P, Delta-1P, and Delta-2P in the C-H oxidation of simple organic molecules can be predicted on the basis of the innate properties of the distinct C-H groups of the substrate. However, in specific complex organic molecules where oxidation of multiple C-H sites is competitive, the highly elaborate structure of the catalysts allows modulation of C-H regioselectivity between the oxidation of tertiary and secondary C-H groups and also among multiple methylene sites, providing oxidation products in synthetically valuable yields. These selectivities complement those accomplished with structurally simpler oxidants, including non-heme iron catalysts Lambda-2 and Lambda-2SbF(6).

  DOI：

  10.1021/jo302196q
• 作为产物：
  描述：

  1-((2R,3aR,9aS,9bR)-3a,6,6,9a-Tetramethyl-dodecahydro-naphtho[2,1-b]furan-2-yl)-ethanone 在 lithium aluminium tetrahydride 、 三氟化硼乙醚 、 sodium acetate 、 间氯过氧苯甲酸 作用下， 以 1,4-二氧六环 、 乙醚 为溶剂， 反应 24.5h， 生成 (-)-ambrox
  参考文献：
  名称：

  由（-）-香紫苏醇高效合成（-）-十二烷基-3a，6,6,9a-四甲基萘[2,1-b]呋喃

  摘要：

  由香紫苏醇2以74％的总产率（3步）制备标题化合物1。关键步骤涉及在香紫苏醇的氧化降解过程中四氧化催化的重排至4a和b。

  DOI：

  10.1016/s0040-4039(00)78188-3

文献信息

• PROCESS FOR THE PREPARATION OF UNSATURATED CARBOXYLIC ACIDS BY CARBONYLATION OF ALLYL ALCOHOLS AND THEIR ACYLATION PRODUCTS
  申请人：BASF SE

  公开号：US20200055834A1

  公开（公告）日：2020-02-20

  The present invention relates to a process for carbonylating allyl alcohols at low temperature, low pressure and/or low catalyst loading. In an alternative embodiment, an acylation product of the allyl alcohol is used for the carbonylation. The present invention likewise relates to the preparation of conversion products of these carbonylation products and specifically of (−)-ambrox.

  本发明涉及一种在低温、低压和/或低催化剂负载下对烯丙醇进行羰基化的过程。在另一实施方式中，烯丙醇的酰化产物被用于羰基化。本发明还涉及制备这些羰基化产物的转化产物，特别是(−)-龙涎香。
• [EN] ORGANIC COMPOUNDS<br/>[FR] COMPOSÉS ORGANIQUES
  申请人：GIVAUDAN SA

  公开号：WO2011073387A1

  公开（公告）日：2011-06-23

  A process for the preparation of β,γ-unsaturated-γ,γ-disubstituted esters 1 with high E/Z- and β,γ/α,β-ratios, Formula (1) by reacting at a temperature of between about 130 and 170 degrees centigrade the conjugated malonate Formula (3) with, a group I, II or III metal halide or an organic cation/halide anion pair, an inorganic proton source and a polar solvent.

  一种制备具有高E/Z-和β,γ/α,β比率的β,γ-不饱和-γ,γ-二取代酯1的方法，通过在约130至170摄氏度的温度下，将共轭马隆酸酯式（3）与I、II或III族金属卤化物或有机阳离子/卤离子对、无机质子源和极性溶剂反应，得到化学式（1）。
• A convenient synthesis of (+)-albicanol based on enzymatic function: total syntheses of (+)-albicanyl acetate, (−)-albicanyl 3,4-dihydroxycinnamate, (−)-drimenol, (−)-drimenin and (−)-ambrox
  作者：Hiroyuki Akita、Masako Nozawa、Ayumi Mitsuda、Hitomi Ohsawa

  DOI：10.1016/s0957-4166(00)00076-8

  日期：2000.4

  enantiomerically pure (+)-albicanyl acetate 3 and (+)-albicanol 4. Deprotection of (+)-3 afforded the natural (+)-albicanol 4 which was converted to the natural products (−)-albicanyl 3,4-dihydroxycinnamate 7, (−)-drimenol 8, (−)-drimenin 9 and (−)-ambrox 10.

  通过使用来自Alcaligenes sp。的脂肪酶“ PL-266” 。用乙酸异丙烯基酯对（±）-白三醇4进行对映体选择性乙酰化，得到对映体纯的乙酸（+）-白三烷基乙酸酯3和（+）-白三醇4。（+）- 3的脱保护得到了天然（+）-白果醇4，其被转化为天然产物（-）-白三烷基3,4-二羟基肉桂酸酯7，（-）-香木酚8，（-）-香木素9和（ −）-ambrox 10。
• Preparation of Ambrox from Labdanes of Dysoxylum hongkongense, and the Preparation of New Diterpenoids from Dysoxylum hongkongense
  申请人：National Taiwan University

  公开号：US20160046593A1

  公开（公告）日：2016-02-18

  The present invention discloses eight new diterpenoids, i.e. Dysongensins A to H, extracted from the leaves and twigs of Dysoxylum hongkongense , wherein AMBROX® which is applicable in the perfume industry is prepared from Dysongensin A via a series of chemical reactions, and the cytotoxicity of Dysongensins A to H against human cancer cell lines and their antiviral and anti-inflammatory activities are determined. Therefore, in the present invention, AMBROX® prepared from Dysongensin A is a new idea for application as an odorous compound in the perfume industry, and the novel diterpenoids can be prepared as a pharmaceutical compositions and/or a drug having antiviral, anti-inflammatory and/or anti-cancer activities.

  本发明揭示了从香港柚木的叶子和枝条中提取的八种新的二萜类化合物，即Dysongensin A至H。其中，通过一系列化学反应从Dysongensin A制备出可应用于香料工业的AMBROX®，并确定了Dysongensin A至H对人类癌细胞系的细胞毒性以及它们的抗病毒和抗炎作用。因此，在本发明中，从Dysongensin A制备的AMBROX®是香料工业中用作气味化合物的新想法，而这些新型二萜类化合物可以制备为具有抗病毒、抗炎和/或抗癌活性的药物组合物和/或药物。
• Process for the Preparation of Optically-Active Compounds
  申请人：Frater Georg

  公开号：US20080064886A1

  公开（公告）日：2008-03-13

  A method of preparing enatiomerically enriched 3a,6,6,9a-tetramethyl-dodecahydro-naphtho[2,1-b]furan, formula (I), from (E,E)-homofarnesic acid or (E)-monocyclohomofarnesic acid by (a) reacting firstly with a chiral alcohol, (b) reacting the product of (a) with an acid to cause a first cyclisation, (c) producing an alcohol by reacting the product of (b) with a reducing agent and (d) causing a second cyclisation by reacting the product of (c) with an acid. The product of this process gives a mixture of both enantiomers with one in excess.

  一种制备对映体富集的3a，6，6，9a-四甲基-十二氢萘[2,1-b]呋喃(I)的方法，该方法从(E,E)-同烯酸或(E)-单环同烯酸开始，包括以下步骤：(a)首先与手性醇反应，(b)将(a)的产物与酸反应以引起第一环化，(c)通过将(b)的产物与还原剂反应生成醇，(d)通过将(c)的产物与酸反应引起第二环化。该过程的产物给出了两个对映体的混合物，一个过量。