(E)-(S)-(+)-1-(trimethylsilyl)-1-octen-3-ol | 120293-89-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-(S)-(+)-1-(trimethylsilyl)-1-octen-3-ol
• 英文别名: (S)-(E)-(+)-1-(Trimethylsilyl)-1-octen-3-ol；(S)-(E)-1-trimethylsilyl-1-octen-3-ol；(S,E)-1-(trimethylsilyl)oct-1-en-3-ol；(E,3S)-1-trimethylsilyloct-1-en-3-ol
• CAS: 120293-89-2
• 化学式: C₁₁H₂₄OSi
• 分子量: 200.396
• InChiKey: UIYNJHZMMWSTOI-USKTWTLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 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)-(S)-(+)-1-(trimethylsilyl)-1-octen-3-ol 在 bis(acetylacetonate)nickel(II) N-溴代丁二酰亚胺(NBS) 、 jones reagent 、 diethylzinc 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 17.08h， 生成 (2S,3R)-(-)-5-oxo-2-pentyltetrahydrofuran-3-carboxylic acid
  参考文献：
  名称：

  Stereoselective Synthesis of Heterocyclic Zinc Reagents via a Nickel-Catalyzed Radical Cyclization

  摘要：

  Unsaturated iodo or bromo acetals of type 2 undergo a smooth cyclization mediated by diethylzinc (2 equiv) and Ni(acac)(2) as catalyst (2-5 mol %). These cyclizations proceed via a radical mechanism affording a (tetrahydrofuranylmethyl)zinc halide of type 1, which can be reacted with various electrophiles after a transmetalation with CuCN . 2LiCl. High stereoselectivities are usually observed in the ring closures, especially if monocyclic cyclization precursors are used. In these cases, bicyclic products of the endo-configuration are obtained with over 94% diastereoselectivity. The synthetic method has been extended to the preparation of a nitrogen heterocycle and over 98% pure trans-4,5-disubstituted gamma-butyrolactones. A short enantioselective synthesis of (-)-methylenolactocine (3) using the radical cyclization and a novel oxidation of alpha-silyl zinc peroxide as a key step is also described.

  DOI：

  10.1021/jo960617s
• 作为产物：
  描述：

  (R)-p-tolyl 2-(trimethylsilyl)ethyl sulfoxide 在 吡啶 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 0.58h， 生成 (E)-(S)-(+)-1-(trimethylsilyl)-1-octen-3-ol
  参考文献：
  名称：

  乙烯基阴离子当量V.使用手性2-（三烷基甲硅烷基）乙基亚砜不对称合成烯丙醇

  摘要：

  光学纯的仲烯丙基醇的两种对映异构体可通过对甲苯基2-（三烷基甲硅烷基）乙基亚砜或叔丁基2-（三甲基甲硅烷基）乙基亚砜的α-亚磺酰基碳负离子与醛随后进行氟化的非对映选择性反应方便地制备。-诱导的亚甲硅烷基亚磺酰基化或亚氨基的热消除。

  DOI：

  10.1016/s0040-4020(01)80816-4

文献信息

• Stereoselective synthesis of 17,18-epoxy derivative of EPA and stereoisomers of isoleukotoxin diol by ring opening of TMS-substituted epoxide with dimsyl sodium
  作者：Yutaro Nanba、Riku Shinohara、Masao Morita、Yuichi Kobayashi

  DOI：10.1039/c7ob02291c

  日期：——

  corresponding mono mesylate was prepared and subjected to epoxide ring formation to afford 17(R),18(S)-EpETE stereoselectively. Similarly, a reaction of the anti epoxy alcohol derived from (R)-1-TMS-1-octen-3-ol with NaDMSO gave the anti form of 1-nonene-3,4-diol, which was converted to 12(S),13(R)-isoleukotoxin diol through Wittig reaction. 12(R),13(R)-Isoleukotoxin diol was synthesized in a similar manner

  TMS取代的环氧醇（及其衍生物）与二甲基钠（NaDMSO）反应生成1-烯烃-3,4-二醇，用于合成对映异构体富集的17（R），18（S）-EpETE和两个异白细胞毒素二醇的非对映异构体。在17（R），18（S）-EpETE的合成中，衍生自（R）-1-TMS-1-戊烯-3-醇的环氧醇的α-乙氧基乙基醚（EE）与NaDMSO反应生成得到单EE保护的1-己烯-3，4-二醇。将通过硼氢化/氧化获得的醛进行Wittig反应，得到单EE-保护的二醇。制备相应的甲磺酸酯并使其形成环环，得到17（R），18（S）-EpETE立体选择。类似地，（R）-1-TMS-1-辛烯-3-醇衍生的抗环氧醇与NaDMSO的反应得到1-壬烯-3,4-二醇的抗形式，其转化为12（S），13（R）-异uk毒素二醇通过Wittig反应。以类似的方式合成了12（R），13（R）-异豆毒素二醇。
• Stereoselective ozonolysis of TMS-substituted allylic alcohol derivatives and synthesis of 14<i>R</i>,15<i>S</i>- and 14<i>S</i>,15<i>S</i>-diHETE
  作者：Shun Saito、Takashi Yamazaki、Yuichi Kobayashi

  DOI：10.1039/c8ob02116c

  日期：——

  contrast, Z-olefins selectively gave the syn isomers with syn/anti ratios of 4–19 : 1. Facial selection was speculated based on the Cieplak effect. This ozonolysis was successfully applied for the synthesis of 14R,15S- and 14S,15S-diHETEs (anti and syn isomers, respectively) in enantioenriched forms.

  TMS取代的烯烃的臭氧分解可产生α-羰基TMS过氧化物，而不会裂解C C键。在此，使用（E）-和（Z）-（1-TMS）alk-1-en-3-ols的甲硅烷基衍生物研究了臭氧分解中的立体化学。（E）异构体经Ph 3 P还原后，提供了主要的立体异构体（抗/ syn = 3–9：1），为抗-3-甲硅烷氧基-2-（TMS-氧基）醛。Z-烯烃选择性生成具有syn / anti的顺式异构体。比例为4：19：1。根据Cieplak效应推测了面部选择。此臭氧分解被成功地应用于14的合成- [R，15小号-和14小号，15小号（-diHETEs抗和顺式在对映体富集形式的分别的异构体，）。
• A short formal synthesis of (−)-methylenolactocin via a nickel catalyzed intramolecular carbozincation
  作者：Andrea Vaupel、Paul Knochel

  DOI：10.1016/0040-4039(94)02243-5

  日期：1995.1

  The lactone 2 which can be converted in one step into (−)-methylenolactocin 1 was prepared in 4 steps, 30 % overall yield and > 92 % ee starting from (E)-3-trimethylsilylpropenal 4. The key step is a new nickel catalyzed cyclization of the polyfunctional bromo-alkenylsilane 3 mediated by Et2Zn. The intermediate organozinc species 7 has been directly oxidized to an aldehyde with oxygen.

  内酯2（ - ） -可被转化在一个步骤中进methylenolactocin 1在4个步骤制备，30％总产率和> 92％ee的由（E）起始-3- trimethylsilylpropenal 4。关键步骤是由Et 2 Zn介导的多官能溴-链烯基硅烷3的新的镍催化环化反应。中间有机锌物质7已被氧气直接氧化为醛。
• Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes
  作者：Roswitha Ostwald、Pierre-Yves Chavant、Heinz Stadtmueller、Paul Knochel

  DOI：10.1021/jo00094a027

  日期：1994.7

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.
• Allylic alcohols of unexpected configuration by oxazaborolidine-catalysed reduction of α,β-unsaturated ketones. An explanation based on MO calculations
  作者：Jordi Bach、Ramon Berenguer、Jaume Farràs、Jordi Garcia、Jordi Meseguer、Jaume Vilarrasa

  DOI：10.1016/0957-4166(95)00357-u

  日期：1995.11

  While the reduction of most alpha,beta-unsaturated ketones with BH3:SMe(2) in the presence of (R)B-methyl-4,5,5-triphenyl-1,3,2-oxazaborolidine [(R)-2] affords allylic alcohols of the S configuration, that of alpha,beta-unsaturated ketones branched at both the alpha and alpha' positions gives alcohols of the R configuration. Theoretical calculations on complexes of representative enones with BH3 (6-31G*) or with BH3:(R)-2 (AMI) may account for the apparent changes in the steric requirements on either side of the CO group.