(1R,2R,4aS,8aS)-(2-hydroxy-2,5,5,8a-tetramethylperhydronaphthyl)acetic acid | 13456-36-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,2R,4aS,8aS)-(2-hydroxy-2,5,5,8a-tetramethylperhydronaphthyl)acetic acid
• 英文别名: 8α-Hydroxy-13,14,15,16-tetranorlabdan-12-oic acid；8α-Hydroxytetra-nor-labda-12-oic acid；8-hydroxy-13,14,15,16-tetranor-labdan-12-oic acid；((4aS)-2c-Hydroxy-2t,5,5,8a-tetramethyl-(4ar,8at)-decahydro-[1t]naphthyl)-essigsaeure；8-Hydroxy-13,14,15,16-tetranor-labdan-12-saeure；((4aS)-2c-Hydroxy-2t.5.5.8at-tetramethyl-(4arH)-decahydro-naphthyl-[1t))-essigsaeure；2-[(1R,2R,4aS,8aS)-2-hydroxy-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydro-1H-naphthalen-1-yl]acetic acid
• CAS: 13456-36-5
• 化学式: C₁₆H₂₈O₃
• 分子量: 268.397
• InChiKey: ASWLRRLLSBVSOH-SHUKQUCYSA-N

物化性质

• 沸点：
  389.9±15.0 °C(Predicted)
• 密度：
  1.035±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2R,4aS,8aS)-(2-hydroxy-2,5,5,8a-tetramethylperhydronaphthyl)acetic acid 在 吡啶 、 三氯氧磷 作用下， 生成 methyl 2-((1S,4aS,8aS)-2,5,5,8a-tetramethyl-1,4,4a,5,6,7,8,8a-octahydronaphthalen-1-yl)acetate
  参考文献：
  名称：

  Carman,R.M.; Deeth,H.C., Australian Journal of Chemistry, 1971, vol. 24, p. 1099 - 1102

  摘要：

  DOI：
• 作为产物：
  描述：

  Bis(8α,13-epoxy-14,15-bisnorlabd-12-en-12-yl)methane 在 sodium hydroxide 、 水 、 臭氧 作用下， 以 乙醇 为溶剂， 反应 3.0h， 生成 (1R,2R,4aS,8aS)-(2-hydroxy-2,5,5,8a-tetramethylperhydronaphthyl)acetic acid
  参考文献：
  名称：

  Synthesis of bicyclohomofarnesane derivatives from bis(8?,13-epoxy-14,15-bisnorlabd-12-en-12-yl)methane ? A product of the ozonolysis of sclareol

  摘要：

  DOI：

  10.1007/bf00630313

文献信息

• Phenylglycine Methyl Ester, a Useful Tool for Absolute Configuration Determination of Various Chiral Carboxylic Acids
  作者：Tetsuya Yabuuchi、Takenori Kusumi

  DOI：10.1021/jo991218a

  日期：2000.1.1

  A new chiral anisotropic reagent, phenylglycine methyl ester (PGME), developed for the elucidation of the absolute configuration of chiral alpha,alpha-disubstituted acetic acids, has turned out to be applicable to other substituted carboxylic acids, such as chiral alpha-hydroxy-, alpha-alkoxy-, and alpha-acyloxy-alpha, alpha-disubstituted acetic acids, as well as to chiral beta, beta-disubstituted

  为了阐明手性α，α-二取代乙酸的绝对构型而开发的一种新的手性各向异性试剂苯甘氨酸甲酯（PGME）已证明可用于其他取代的羧酸，例如手性α-羟基- ，α-烷氧基-和α-酰氧基-α，α-二取代的乙酸，以及手性β，β-二取代的丙酸。由于羧基部分可从其他官能团转化而来，例如烯烃的臭氧分解和二醇的氧化裂解，因此，本发现可将PGME方法的用途扩展到各种类型有机化合物的绝对构型测定，甚至那些最初缺乏氧气功能。描述了化学反应和PGME方法结合的几个例子。
• Making Fe(BPBP)-catalyzed C–H and CC oxidations more affordable
  作者：Vital A. Yazerski、Peter Spannring、David Gatineau、Charlotte H. M. Woerde、Sara M. Wieclawska、Martin Lutz、Henk Kleijn、Robertus J. M. Klein Gebbink

  DOI：10.1039/c3ob42249f

  日期：——

  The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α-[Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf)2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C–H and CC bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C–H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude DL/meso-2,2′-bipyrrolidine. Next to its use in C–H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.

  催化反应组分的有限可用性可能成为许多催化过程在有机合成中实际应用的主要障碍。本工作中,我们证明了由异构铁配合物[Fe(OTf)2(mix-BPBP)] (mix-1)组成的混合物,包括λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1)、Δ-α-[Fe(OTf)2(R,R-BPBP)] (R,R-1)和Δ/λ-β-[Fe(OTf)2(R,S-BPBP)] (R,S-1),是使用过氧化氢作为氧化剂对包括模型烃和光学纯天然产物在内的各种脂肪族化合物进行制备氧化的实用催化剂。在mix-1中存在的物种中,S,S-1和R,R-1是催化活性的,独立作用,约占mix-1的75%。剩余的25%由介观R,S-1代表,名义上在C–H和CC键氧化反应中起旁观者作用。总体而言,这种铁配合物混合物显示出与其先前分别用于sp3 C–H氧化的纯对映体组分相同的催化特征。与它们不同的是,mix-1可通过从粗DL/中二吡咯烷的两个高产率步骤大量制备。除了用于C–H氧化外,mix-1在化学选择性环氧化反应中也表现出活性,这使我们能够开发出一种用于环氧化合物合成的实用催化方案。
• [EN] A PROCESS FOR THE OPTICAL RESOLUTION OF A PRECURSOR OF SCLAREOLIDE<br/>[FR] PROCEDE DE RESOLUTION OPTIQUE D'UN PRECURSEUR DU SCLAREOLIDE
  申请人：FIRMENICH & CIE

  公开号：WO2004013069A1

  公开（公告）日：2004-02-12

  The present invention relates to the field of organic synthesis and more particularly to a new process for the optical resolution of a precursor of sclareolide. Said process is characterized by the reaction of [(1RS,2RS,4aSR,8aSR)-2-hydroxy-2,5,5,8a-tetramethyldecahydronaphthalen-1-yl]acetic acid, or an alkaline salt thereof, with an enantiomer of the 2-(methylamino)-1-phenyl-1-propanol, or an ammonium salt thereof respectively, which is used as resolving agent.

  本发明涉及有机合成领域，更具体地涉及一种用于光学分辨前驱物斯氯酮酸的新工艺。该工艺的特点是将[(1RS,2RS,4aSR,8aSR)-2-羟基-2,5,5,8a-四甲基癸氢萘-1-基]乙酸或其碱盐与2-(甲胺基)-1-苯基-1-丙醇的对映体或其铵盐分别反应，后者用作分离剂。
• [EN] PROCESS FOR THE CYCLODEHYDRATION OF DIOLS AND USE THEREOF FOR THE MANUFACTURING OF AMBRAFURAN AND OTHER CYCLOETHER DERIVATIVES<br/>[FR] PROCÉDÉ DE CYCLODÉSHYDRATATION DE DIOLS ET SON UTILISATION POUR LA FABRICATION D'AMBRAFURANE ET D'AUTRES DÉRIVÉS DE CYCLOÉTHERS
  申请人：KOSTE BIOCHEMICALS

  公开号：WO2013007832A1

  公开（公告）日：2013-01-17

  The present invention relates to a process for manufacturing tetrahydrofuran, tetrahydropyran and, more generally, cycloether derivatives through the cyclodehydration of 1,4- or 1,5- diols. More specifically, the process of the invention involves (i) the stereoselective cyclodehydration in water of 1,4- or 1,5- diols comprising at least one chiral tertiary alcohol functional group with retention of the initial chirality, and/or (ii) the cyclodehydration in water of 1,4- or 1,5- diols, said diols being non-miscible with and/or non-soluble in water, into corresponding cycloether derivatives, by bringing the reaction mixture to high temperature water (HTW) conditions and/or by mixing the aqueous reaction mixture with a solid catalyst, such as for example a smectite clay. The present invention further relates to the use of the process of the invention for manufacturing ambrafuran, especially (-)-ambrafuran and other cycloether derivatives.

  本发明涉及通过1,4-或1,5-二醇的环缩水合反应制备四氢呋喃、四氢吡喃和更一般的环醚衍生物的方法。具体而言，本发明的方法包括：(i)在水中立体选择性地环缩水合含有至少一个手性三级醇官能团的1,4-或1,5-二醇，保持初始手性；和/或(ii)在水中环缩水合1,4-或1,5-二醇，所述二醇不与水相容和/或不溶于水，形成相应的环醚衍生物，通过将反应混合物带到高温水（HTW）条件和/或通过将水溶反应混合物与固体催化剂混合，例如蒙脱石粘土。本发明还涉及使用本发明的方法制备琥珀香呋喃，特别是(-)-琥珀香呋喃和其他环醚衍生物。
• Odeur et constitution IV. Sur les époxydes hydroaromatiques à odeur ambrée
  作者：M. Hinder、M. Stoll

  DOI：10.1002/hlca.19500330527

  日期：——

  La réduction de la lactone I, de l'hydroxyacide VI, de l'acétoxyacide VII ou de l'ozonide de l'oxyde non saturé XII par l'hydrure de lithium-aluminium donne le glycol II avec un bon rendement.

  内酯I，羟基丙酸VI，羟基乙酸VII或不饱和的氧代十二烷基苯磺酸铝锂II胶粘剂。