(2S,3S)-1-O-benzyl-2,3-epoxygeraniol | 306775-68-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S)-1-O-benzyl-2,3-epoxygeraniol
• 英文别名: (2S,3S)-2-methyl-2-(4-methylpent-3-enyl)-3-(phenylmethoxymethyl)oxirane
• CAS: 306775-68-8
• 化学式: C₁₇H₂₄O₂
• 分子量: 260.376
• InChiKey: CTNVUJMSFFLEHB-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-1-O-benzyl-2,3-epoxygeraniol 在 palladium dihydroxide 、 palladium on activated charcoal 吡啶 、 chromium dichloride 、 高氯酸 、 氢气 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 rhenium(VII) oxide 、 三氟乙酸酐 、 nickel dichloride 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 、 乙腈 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 77.75h， 生成 (+)-Thyrsiferol
  参考文献：
  名称：

  Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis

  摘要：

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.

  DOI：

  10.1021/ja000001r
• 作为产物：
  描述：

  3-(benzo[d]thiazol-2-ylsulfonyl)-5-(3-(benzyloxymethyl)-2-methyloxiran-2-yl)-2-methylpentan-2-ol 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以70%的产率得到(2S,3S)-1-O-benzyl-2,3-epoxygeraniol
  参考文献：
  名称：

  将环氧化物转化为烯烃的新方法

  摘要：

  环氧化物已通过以下过程以良好的收率转化为烯烃，包括 (i) 环氧化物与 2-巯基苯并噻唑的开环，(ii) 衍生的 s-羟基硫醚氧化为相应的砜，以及 (iii) 热或碱- 促进这些砜碎裂成烯烃。由于 SN2 环氧化物开环反应和 s-烷氧基亚磺酸盐中间体的反周面 SO2 消除反应，起始环氧化物的立体化学忠实地转移到烯烃产物上。这种方法可能构成新的烯烃保护基策略的基础。© 2010 Wiley-VCH Verlag GmbH & Co. KGaA。

  DOI：

  10.1002/ejoc.200901264

文献信息

• Atom-Economic and Stereoselective Syntheses of the Ring A and B Subunits of the Bryostatins
  作者：Barry M. Trost、Hanbiao Yang、Cheyenne S. Brindle、Guangbin Dong

  DOI：10.1002/chem.201002930

  日期：2011.8.22

  subunits of bryostatins. A Ru‐catalyzed tandem alkene–alkyne coupling/Michael addition reaction was developed and applied to the synthesis of bryostatin ring B. We explored an acetylide‐mediated epoxide‐opening/6‐exo‐dig cyclization route to access the bryostatin ring A, although ring A was eventually furnished through an acid‐catalyzed tandem transketalization/ketalization sequence. In addition, a dinuclear

  本文描述了苔藓抑素环 A 和 B 亚基立体选择性组装的化学选择性和原子经济方法。钌催化的串联烯烃-炔耦合/迈克尔加成反应的开发和应用到苔藓抑素环B的合成我们探讨乙炔化介导的环氧化物的开/ 6-外型-挖环化路径访问的苔藓抑素环A，虽然环 A 最终通过酸催化的串联转缩酮/缩酮化序列提供。此外，还评估了双核锌催化甲基乙烯基酮（MVK）羟醛策略用于构建聚乙酸酯部分。这些方法的使用最终导致了包含环 A 和 B 亚基的北部苔藓抑素片段的快速组装。
• Enantioselective Synthesis of Pladienolide B and Truncated Analogues as New Anticancer Agents
  作者：Vemula Praveen Kumar、Srivari Chandrasekhar

  DOI：10.1021/ol401458d

  日期：2013.7.19

  An enantioselective synthesis of natural anticancer macrolide pladienolide B is described. The synthetic highlights include Sharpless asymmetric epoxidation, ring closing metathesis (RCM), Ireland–Claisen rearrangement, Shi epoxidation, and Pd-catalyzed Stille coupling as key steps. The synthetic route also allowed the synthesis of the truncated analogues (41a–d) of pladienolide B.

  描述了天然抗癌大环内酯大环内酯B的对映选择性合成。合成亮点包括Sharpless不对称环氧化，闭环复分解（RCM），爱尔兰–克莱森重排，Shi环氧化和Pd催化的Stille偶联等关键步骤。合成途径还允许合成普拉二烯内酯B的截短类似物（41a – d）。
• Stereospecific and efficient alkynylation at the more hindered carbon of trisubstituted epoxidesElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b3/b308204k/
  作者：Hongda Zhao、Brian L. Pagenkopf

  DOI：10.1039/b308204k

  日期：——

  The stereospecific and regioselective C(3) alkynylation of trisubstituted epoxides has been achieved with lithium alkynyl trimethylaluminium ate complexes in the presence of BF3·OEt2.

  在 BF3-OEt2 的存在下，利用炔基三甲铝锂 ate 复合物实现了三取代环氧化物的立体特异性和区域选择性 C(3) 烷基化反应。
• Reactions of alanes and aluminates with tri-substituted epoxides. Development of a stereospecific alkynylation at the more hindered carbon
  作者：Hongda Zhao、Darren W. Engers、Christian L. Morales、Brian L. Pagenkopf

  DOI：10.1016/j.tet.2007.06.036

  日期：2007.9

  The addition of 4 equiv of phenyl ethynyl dimethyl alane (formed by treatment of phenyl acetylene with n-BuLi followed by Me2AlCl) to 2,3-epoxy geraniol results in the formation of the C-3 alkynyl addition product and the Yamamoto rearrangement/addition product, in 53 and 18% yield, respectively. Replacing the alane reagent with an aluminate (formed by treatment of phenyl acetylene with n-BuLi followed by Me3Al) and adding BF3. OEt2 result in formation of the C-3 addition product in 73% yield. (c) 2007 Elsevier Ltd. All rights reserved.
• Useful base promoted elaborations of oxiranyl ethers
  作者：Angelika Thurner、Ferenc Faigl、László Tőke、Alessandro Mordini、Michela Valacchi、Gianna Reginato、Gábor Czira

  DOI：10.1016/s0040-4020(01)00790-6

  日期：2001.9

  Functionalized oxiranyl ethers can be regio- and stereoselectively converted into hydroxy oxetanes or cis-diols by treatment with organometallic bases. These two rearrangements can be conveniently carried out either using different reaction conditions starting from the oxirane or in two consecutive steps from the oxirane via the oxetane. (C) 2001 Elsevier Science Ltd. All rights reserved.