(±)-ambrox | 3738-00-9

• 物质功能分类: 有机原料 - 醚类化合物及其衍生物
• 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: rac-ambrox；(3aS,5aR,9aR,9bS)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran
• CAS: 3738-00-9；6790-58-5；67844-43-3；68365-88-8；68365-89-9；100679-85-4；105561-31-7；108945-29-5；119818-38-1；122566-15-8；122566-16-9；122566-18-1；124578-52-5；131831-61-3；131831-62-4；131831-63-5；133907-53-6；138283-79-1；138283-80-4；145164-17-6
• 化学式: C₁₆H₂₈O
• 分子量: 236.398
• InChiKey: YPZUZOLGGMJZJO-CLWVCHIJSA-N

物化性质

• 熔点：
  75-76 °C
• 沸点：
  273.9±8.0 °C(Predicted)
• 密度：
  0.939±0.06 g/cm3(Predicted)
• LogP：
  5.41

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

安全信息

• 海关编码：
  2932999099

制备方法与用途

生产方法主要采用紫苏醇作为起始原料。

反应信息

• 作为反应物：
  描述：

  (±)-ambrox 在 C₁₇H₂₁FeN₅O₅^(1-) 、 水 作用下， 以 aq. phosphate buffer 、 乙腈 为溶剂， 反应 10.0h， 以75%的产率得到(+/-)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldecahydronaphtho[2,1-b]furan-2-one
  参考文献：
  名称：

  Oxoiron（V）以水为氧气源，介导未活化的C–H和CC键的选择性电化学氧化

  摘要：

  使用仿生铁络合物[（bTAML）Fe III -OH 2 ] -选择性氧化未活化烷烃（BDE≤97kcal mol -1）的C–H键和烯烃的C C键的有效电化学方法据报道，作为具有廉价碳和镍电极的不分隔电化学电池中的氧化还原介体。水的O原子仍然是氧化后形成的产品中O掺入的来源。由C–H键氧化形成的产物具有很高的区域选择性（金刚烷为75：1、3°：2°）和立体保留（对于环己烷衍生物，RC约为99％）。底物的范围包括天然产物，例如乙酸双乙酰丁酯和过氧化氢。对于烯烃，环氧化物是唯一的产物。机理研究显示出高的价oxoiron的参与（V）物种，[（bTAML）的Fe V（O）] -形成经由PCET（总2H + / 2E - ）从[（bTAML）铁III -OH 2 ] -在CPE中于0.80 V（相对于Ag / AgNO 3）。此外，对C–H键氧化的电动学研究表明，由氧代铁（ V）提取C–H的二级反应是决定速率的步骤。

  DOI：

  10.1039/d0sc03616a
• 作为产物：
  描述：

  4-(2,2-二甲基-6-亚甲基环己基)丁烷-2-酮 在 正丁基锂 、 氟磺酸 作用下， 以 various solvent(s) 为溶剂， 反应 23.0h， 生成 (±)-ambrox
  参考文献：
  名称：

  Internal nucleophilic termination in biomimetic acid mediated polyene cyclizations: stereochemical and mechanistic implications. Synthesis of (.+-.)-Ambrox and its diastereoisomers

  摘要：

  Treatment of 10 structurally related trienols and dienols 5-8 with an excess of fluorosulfonic acid in 2-nitropropane at -90-degrees-C afforded, in 74-87% yield, diastereoisomeric mixtures of the odoriferous norlabdane oxides 9-15 ((-)-9 (Ambrox) is a naturally occurring ambergris odorant). These transformations represent examples of efficient biomimetic acid-mediated cyclizations in which the hydroxyl group serves as the internal nucleophilic terminator. The stereochemical outcome of these kinetically controlled processes has been analysed in detail, and mechanistic hypotheses consistent with the results have been proposed. For the four acyclic trienols 5, the major reaction pathway can be rationalized by a totally synchronous process involving three internal anti additions via chair or skew-boat conformations of the nascent cyclohexane rings. An alternative explanation postulates a non-synchronous process in which ring closure to an intermediate cyclohexyl cation is followed by rapid cyclization, directed by a strong kinetic preference for equatorial C-C and C-O ond formation. In contrast, for the monocyclic dienols 6-8 only a nonsynchronous process, involving prior protonation of the cyclohexenyl bond, is fully consistent with the results. In the nonsynchronous processes, the orientation of the side chain vicinal to the cyclohexyl cation directs the stereochemical course of the cyclization. For the acyclic trienols, this factor is predetermined by the configuration of the C(7) = C(8) bond, whereas, for the acyclic trienols, this factor is predetermined by the configuration of the C(7) = C(8) bond, whereas, for the monocyclic dienols, this orientation is determined by the stereoselective axial protonation of the cyclohexenyl bond in 6, or by the distribution of cyclohexene and cyclohexane conformers in 7 and 8, respectively. In the cases studied, it is clear that conformational inversion of the six-membered ring is slower than cyclization and thus ensures that an equatorial side chain leads to a trans A/B ring junction in the cyclization product, whereas an axial side chain affords a cis A/B ring junction.

  DOI：

  10.1021/jo00029a031

文献信息

• Photochemically induced radical alkynylation of C(sp³)–H bonds
  作者：Tamaki Hoshikawa、Shin Kamijo、Masayuki Inoue

  DOI：10.1039/c2ob26785c

  日期：——

  C(sp3)–H bonds has been developed. After C–H abstraction by the photo-excited benzophenone, a two-carbon unit was efficiently transferred to the generated radical from 1-tosyl-2-(trimethylsilyl)acetylene to afford the alkynylated product. The present reaction enables construction of various tri- and tetra-substituted carbons from heteroatom-substituted methylenes, methines and alkanes in a highly chemoselective

  已经开发出一种用于光化学炔化未反应的C（sp 3）–H键的通用策略。通过光激发的二苯甲酮将C–H抽象化后，一个两碳单元被有效地转移至由1-甲苯磺酰基-2-（三甲基甲硅烷基）乙炔得到炔基化产物。本反应使得能够以高度化学选择性的方式由杂原子取代的亚甲基，次甲基和烷烃构造各种三和四取代的碳，并且将用作快速构建复杂结构的新合成策略。
• [EN] PROCESS FOR THE PREPARATION OF OPTICALLY-ACTIVE COMPOUNDS<br/>[FR] PROCEDE POUR PREPARER DES COMPOSES OPTIQUEMENT ACTIFS
  申请人：GIVAUDAN SA

  公开号：WO2006010287A1

  公开（公告）日：2006-02-02

  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.

  使用(E,E)-同烯基烯酸或(E)-单环同烯基烯酸制备富含对映体的3a,6,6,9a-四甲基-十二氢-萘[2,1-b]呋喃（化学式(I)）的方法包括：(a)首先与手性醇反应，(b)将(a)的产物与酸反应以引发第一环化反应，(c)通过将(b)的产物与还原剂反应产生醇，(d)通过将(c)的产物与酸反应引发第二环化反应。该过程的产物给出了两种对映体的混合物，其中一种过量。
• Enantio- and Diastereoselective Stepwise Cyclization of Polyprenoids Induced by Chiral and Achiral LBAs. A New Entry to (−)-Ambrox, (+)-Podocarpa-8,11,13-triene Diterpenoids, and (−)-Tetracyclic Polyprenoid of Sedimentary Origin
  作者：Kazuaki Ishihara、Hideaki Ishibashi、Hisashi Yamamoto

  DOI：10.1021/ja0124865

  日期：2002.4.1

  stepwise cyclization of polyprenoids induced by Lewis acid-assisted chiral Brønsted acids (chiral LBAs) and achiral LBAs is described. In particular, the absolute stereocontrol in the initial cyclization of polyprenoids to form an A-ring induced by chiral LBAs and the importance of the nucleophilicity of the internal terminator in polyprenoids for the relative stereocontrol in subsequent cyclization are

  描述了由路易斯酸辅助的手性布朗斯台德酸（手性 LBA）和非手性 LBA 诱导的聚异戊二烯的对映选择性和非对映选择性逐步环化。特别是，证明了在聚异戊二烯初始环化以形成由手性 LBA 诱导的 A 环中的绝对立体控制，以及聚异戊二烯中内部终止子的亲核性对于后续环化中的相对立体控制的重要性。(-)-Ambrox 通过 (E,E)-高法呢基三乙基甲硅烷基醚与氯化锡 (IV) 配位的 (R)-2-(o-氟苄氧基)-2'-羟基-1,1' 的对映选择性环化反应合成-联萘 ((R)-BINOL-o-FBn) 和随后的非对映选择性环化与 CF(3)CO(2)H.SnCl(4) 作为关键步骤。保护 (E, E)-由三乙基甲硅烷基组成的高法呢醇增加了手性 LBA 诱导的环化的对映选择性以及随后环化中的化学产率和非对映选择性。(R)-BINOL-o-FBn.SnCl(4) 还诱导了具有芳基的均（聚异戊二烯基）芳烃的对映选择性环化。通过
• Selective photocatalytic hydroxylation and epoxidation reactions by an iron complex using water as the oxygen source
  作者：Bittu Chandra、Kundan K. Singh、Sayam Sen Gupta

  DOI：10.1039/c7sc02780j

  日期：——

  [(bTAML)FeIII–OH2]− (1) selectively catalyses the photocatalytic hydroxylation and epoxidation reactions of alkanes and alkenes, respectively, using water as the oxygen-atom source. Upon the oxidation of unactivated alkanes, which included several substrates including natural products, hydroxylation was observed mostly at the 3° C–H bonds with 3°:2° selectivity up to ∼100:1. When alkenes were used as the substrates

  铁络合物[（bTAML）Fe III -OH 2 ] -（1）分别使用水作为氧原子源，分别选择性催化烷烃和烯烃的光催化羟基化和环氧化反应。在未活化的烷烃被氧化后，其中包括几种包括天然产物在内的底物，大多数情况下在3°C–H键上观察到羟基化，选择性高达3 ：2 ：2，直至约100 ：1。当使用烯烃作为底物时，环氧化物主要以高产形成。在H存在2 18 O，90％以上的的18O标记的氧原子被掺入羟基化和环氧产物中，表明水是主要的氧源。机理研究表明，起始的复合物1通过PCET形成了活性的[（bTAML）Fe IV } 2 - μ-氧代] 2-（2）二聚体。添加底物时随后的歧化2导致形成Fe V（O），从而在这些反应中观察到高选择性。
• [EN] PROCESS FOR THE PREPARATION OF TETRANORLABDANE DERIVATIVES<br/>[FR] PROCÉDÉ POUR LA PRÉPARATION DE DÉRIVÉS DE TÉTRANORLABDANE
  申请人：FIRMENICH & CIE

  公开号：WO2009053883A1

  公开（公告）日：2009-04-30

  The present invention concerns a process for the preparation of a compound of formula (I), wherein the dotted line is a single bond and n is 1 or the dotted line is a double bond and n is 0, and wherein the relative configuration is as shown, in the form of any one of its diastereoisomers or enantiomers or mixtures thereof.

  本发明涉及一种制备式(I)化合物的方法，其中虚线是单键，n为1，或者虚线是双键，n为0，相对构型如所示，以其任一对映异构体或对映体或其混合物的形式。