(E)-(2R,4S,8R)-2,4,6,8-tetramethyl-6-decen-1-ol | 273738-39-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-(2R,4S,8R)-2,4,6,8-tetramethyl-6-decen-1-ol
• 英文别名: (2R,4S,6E,8R)-2,4,6,8-tetramethyldec-6-en-1-ol；(2R,4S,8R,E)-2,4,6,8-tetramethyl-6-decen-1-ol；(2R,4S,8R,E)-2,4,6,8-tetramethyldec-6-en-1-ol；(2R,4R,6E,8R)-tetramethyl-6-decen-1-ol；(E,2R,4S,8R)-2,4,6,8-tetramethyldec-6-en-1-ol
• CAS: 273738-39-9
• 化学式: C₁₄H₂₈O
• 分子量: 212.376
• InChiKey: DGKFGNWXKFTWCM-MSMVHNDYSA-N

物化性质

• 沸点：
  281.3±9.0 °C(Predicted)
• 密度：
  0.843±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-(2R,4S,8R)-2,4,6,8-tetramethyl-6-decen-1-ol 在 potassium fluoride 、 N-甲基吲哚酮 、 四丙基高钌酸铵 、 Florisil 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 (2E,4E,6E,12E)-(8R,10S,14R)-8,10,12,14-(tetramethyl)hexadeca-2,4,6,12-tetraenoic acid ethyl ester
  参考文献：
  名称：

  Synthesis (and Alternative Proof of Configuration) of the Scyphostatin C(1‘)−C(20‘) Trienoyl Fragment

  摘要：

  [GRAPHICS]Each of four diastereomers of structure 2, corresponding to the lipophilic side chain of scyphostatin (1), were prepared. Careful analysis of their NMR spectral data and comparison with those of the natural product corroborates the recently reported (Org. Lett. 2000, 2, 505) stereochemical assignment. A strategy for the stereoselective synthesis of 2 has been achieved.

  DOI：

  10.1021/ol0058386
• 作为产物：
  描述：

  2-甲基丁醇 在 pseudomonas fluorescens lipase 正丁基锂 、 乙酸乙烯酯 、 二氯二茂锆 、 草酰氯 、 四丁基氟化铵 、 叔丁基锂 、 三乙基硼氢化锂 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 various solvents 为溶剂， 反应 6.5h， 生成 (E)-(2R,4S,8R)-2,4,6,8-tetramethyl-6-decen-1-ol
  参考文献：
  名称：

  An improved synthesis of the scyphostatin side-chain

  摘要：

  A formal synthesis of the lipophilic side-chain of scyphostatin has been achieved using a convergent synthesis, in 16% yield over,six steps. This synthesis involves enzymatic desymmetrisation of a meso-diol, resolution of 2-methylbutan-1-ol, stereoselective hydrozirconation of a volatile acetylene and a Negishi-style cross coupling. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.01.156

文献信息

• Highly (≥98%) Stereo- and Regioselective Trisubstituted Alkene Synthesis of Wide Applicability via 1-Halo-1-alkyne Hydro- boration-Tandem Negishi-Suzuki Coupling or Organoborate Migratory Insertion
  作者：Shiqing Xu、Ching-Tien Lee、Honghua Rao、Ei-ichi Negishi

  DOI：10.1002/adsc.201100420

  日期：2011.11

  synthetic utility of the present methodology has been demonstrated in the highly selective synthesis of side chain (4) of scyphostatin in 28% yield over nine steps in the longest linear sequence from allyl alcohol. Thus, this new tandem protocol has been emerged as the most widely applicable and highly selective route to trisubstituted alkenes including those that are otherwise difficult to prepare.

  然后用有机锂或格氏试剂处理以产生具有反向立体构型的三取代烯烃。本方法的合成效用已在从烯丙醇以最长线性序列的九个步骤以 28% 的收率高选择性合成 scyphostatin 的侧链 (4) 中得到证明。因此，这种新的串联方案已成为最广泛适用和高度选择性的三取代烯烃路线，包括那些难以制备的烯烃。
• Stereoselective Synthesis of the Hydrophobic Side Chain of Scyphostatin
  作者：Ryukichi Takagi、Shinjiro Tsuyumine、Hiroko Nishitani、Wataru Miyanaga、Katsuo Ohkata

  DOI：10.1071/ch03298

  日期：——

  The hydrophobic side chain of scyphostatin was synthesized by a convergent synthetic pathway. The key reactions were the enzymatic asymmetric acetylation of a meso-diol, construction of the C12′–C13′ trisubstituted E-olefin moiety by Negishi coupling, and construction of the (2′E,4′E ,E,6′E)-triene moiety by Horner–Wadsworth–Emmons olefination.

  scyphosstatin的疏水侧链是通过聚合合成途径合成的。关键反应是内消旋二醇的酶促不对称乙酰化，通过 Negishi 偶联构建 C12'-C13' 三取代的 E-烯烃部分，以及构建 (2'E,4'E ,E,6'E)霍纳-沃兹沃思-埃蒙斯烯化的-三烯部分。
• Total synthesis of (+)-scyphostatin featuring an enantioselective and highly efficient route to the side-chain via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)
  作者：Emmanuel Pitsinos、Nikolaos Athinaios、Zhaoqing Xu、Guangwei Wang、Ei-ichi Negishi

  DOI：10.1039/b920261g

  日期：——

  (+)-Scyphostatin (1) was synthesized via (i) construction of a side-chain 3b of > or = 98% purity in 19% yield in eleven steps featuring ZACA reaction, Negishi coupling, and HWE olefination, (ii) an asymmetric synthesis of a fully protected core 4 from 10a, and (iii) a three-step assembly of 1 in 42% yield.

  （+）-Scyphostatin（1）通过（i）以ZACA反应，Negishi偶联和HWE烯化为特征的11个步骤构建纯度≥98％或纯度为98％，收率为19％的侧链3b，（ii）由10a不完全合成完全受保护的核4，以及（iii）以42％的收率得到1的三步组装。
• Enantioselective Total Synthesis of (+)-Scyphostatin, a Potent and Specific Inhibitor of Neutral Sphingomyelinase
  作者：Tadashi Katoh、Munenori Inoue、Wakako Yokota

  DOI：10.1055/s-2007-965893

  日期：2007.2

  The total synthesis of (+)-scyphostatin, a specific and potent neutral sphingomyelinase inhibitor from a microorganism, was accomplished for the first time starting from D-arabinose and both enantiomers of methyl 3-hydroxy-2-methylpropionate. The method involves (a) stereoselective aldol coupling of a methyl 1,3-dioxolane-4-carboxylate with the Garner aldehyde to establish the asymmetric quaternary

  (+)-scyphosstatin 是一种来自微生物的特异性和有效的中性鞘磷脂酶抑制剂，首次从 D-阿拉伯糖和 3-羟基-2-甲基丙酸甲酯的两种对映异构体开始完成全合成。该方法包括 (a) 1,3-二氧戊环-4-羧酸甲酯与 Garner 醛的立体选择性羟醛偶联，以在 C4 处建立不对称季碳中心，(b) 所得二烯的闭环复分解以构建环己烯环，(c) 乙烯基碘化物和烷基碘化物的 Negishi 偶联以形成必需的三取代的 E-烯烃，(d) 从环己烯链段和三取代的 E-烯烃脂肪酸链段形成酰胺，和 (e) 立体定向由两个链段形成的酰胺的甲磺酸酯形成环氧环。
• Synthesis (and Alternative Proof of Configuration) of the Scyphostatin C(1‘)−C(20‘) Trienoyl Fragment
  作者：Thomas R. Hoye、Manomi A. Tennakoon

  DOI：10.1021/ol0058386

  日期：2000.5.1

  [GRAPHICS]Each of four diastereomers of structure 2, corresponding to the lipophilic side chain of scyphostatin (1), were prepared. Careful analysis of their NMR spectral data and comparison with those of the natural product corroborates the recently reported (Org. Lett. 2000, 2, 505) stereochemical assignment. A strategy for the stereoselective synthesis of 2 has been achieved.