(S)-3-octyn-2-ol

• 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: (S)-3-octyn-2-ol
• 英文别名: (S)-oct-3-yn-2-ol；(2S)-oct-3-yn-2-ol
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: RRRODBVLAIUQDT-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (S)-3-octyn-2-ol 在 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 (R)-N-(oct-3-yn-2-yl)-N-benzylamine
  参考文献：
  名称：

  PdCl₂-Catalyzed Efficient Transformation of Propargylic Amines to (E)-α-Chloroalkylidene-β-lactams

  摘要：

  The PdCl2-catalyzed cyclocarbonylation reaction of propargylic amines with CuCl2 and benzoquinone afforded (E)-alpha-chloroalkylidene-beta-lactams in moderate to good yields. The formation of the corresponding Z-isomers or five-membered products was not observed. The reaction of the readily available optically active propargylic amines provides a convenient synthesis of the corresponding (E)-alpha-chloroalkylidene-beta-lactams with high ee values. The structure and the stereochemistry of the products were established by the X-ray single-crystal diffraction study of (E)-6d and (E)-6e, which indicates that the stereoselectivity in this reaction is different from what was observed with propargylic alcohols. A rationale for this reaction was proposed.

  DOI：

  10.1021/jo0480996
• 作为产物：
  描述：

  在 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 作用下， 生成 (S)-3-octyn-2-ol
  参考文献：
  名称：

  炔丙醇的高度对映选择性合成

  摘要：

  在硅上带有手性助剂的甲硅烷基炔丙基碳负离子已被烷基化，具有出色的区域选择性和非对映选择性。已经研究了溶剂的作用并且已经以高对映体过量合成了炔丙醇。

  DOI：

  10.1016/s0040-4039(00)60315-5

文献信息

• Asymmetric [2,3]-Wittig Rearrangement: Synthesis of Homoallylic, Allenylic, and Enynyl α-Benzyl Alcohols
  作者：Ricardo I. Rodríguez、Elsie Ramírez、José A. Fernández-Salas、Rubén Sánchez-Obregón、Francisco Yuste、José Alemán

  DOI：10.1021/acs.orglett.8b03659

  日期：2018.12.21

  A highly stereoselective [2,3]-Wittig rearrangement of allylic and propargylic ethers controlled by a chiral sulfoxide moiety is presented. The activation provided by the sulfoxide at the remote ortho position allows the rearrangement of less-activated and unexplored benzylic carbanions. Thus, this general methodology gives access to the asymmetric synthesis of homoallylic, enynyl, and allenylic α-benzyl

  呈现了由手性亚砜部分控制的烯丙基和炔丙基醚的高度立体选择性[2,3] -Wittig重排。亚砜在遥远的邻位提供的活化作用使未活化和未开发的苄基碳负离子得以重排。因此，这种通用方法使不对称合成均烯丙基，烯丙基和烯丙基α-苄醇衍生物成为可能。
• Copper(I)-Catalyzed Regio- and Chemoselective Single and Double Addition of Nucleophilic Silicon to Propargylic Chlorides and Phosphates
  作者：Chinmoy K. Hazra、Martin Oestreich

  DOI：10.1021/ol301827t

  日期：2012.8.3

  Copper(I)-catalyzed propargylic substitution of linear precursors with (Me2PhSi)2Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me2PhSi)2Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride

  铜（I）催化的线性前驱物被（Me 2 PhSi）2 Zn取代的线性前驱体主要产生独立于炔丙基离去基团的γ异构体。如此形成的烯丙基硅烷与另一当量的（Me 2 PhSi）2 Zn区域选择性地反应，从而产生具有烯丙基和乙烯基硅基团的双官能结构单元。对于氯化物（γ：α≥99：1），这两个步骤的反应速率都非常平衡，在该步骤中，炔丙基位移在添加步骤之前定量发生。还报道了α-支链的炔丙基磷酸酯的取代。
• Copper-Catalyzed γ-Selective and Stereospecific Substitution Reaction of Allylic Carbonates with Diboron:  Efficient Route to Chiral Allylboron Compounds
  作者：Hajime Ito、Chika Kawakami、Masaya Sawamura

  DOI：10.1021/ja056099x

  日期：2005.11.23

  copper-catalyzed gamma-selective and stereospecific substitution reaction of allylic carbonates with a diboron reagent affording allylboron compounds is described. Boryl group was selectively introduced at the gamma-position of the leaving carbonate group. Functionalized allylboronates that have an acetal, ester, or isolated alkene were prepared. The reaction of optically active allylic carbonates underwent complete

  描述了铜催化的 γ 选择性和立体定向取代反应烯丙基碳酸酯与二硼试剂提供烯丙基硼化合物。在离去碳酸酯基团的 γ 位选择性地引入硼基。制备了具有缩醛、酯或分离的烯烃的官能化烯丙基硼酸酯。旋光烯丙基碳酸酯的反应通过反立体化学进行完全的 α 到 γ 手性转移，以​​产生具有硼取代立体中心的旋光烯丙基硼酸酯。
• Copper-Catalyzed γ-Selective and Stereospecific Allyl−Aryl Coupling between (<i>Z</i>)-Acyclic and Cyclic Allylic Phosphates and Arylboronates
  作者：Hirohisa Ohmiya、Natsumi Yokokawa、Masaya Sawamura

  DOI：10.1021/ol100841y

  日期：2010.5.21

  A Cu-catalyzed allyl−aryl coupling reaction between (Z)-acyclic or cyclic allylic phosphates and arylboronates proceeds with excellent γ-E-selectivity and 1,3-anti chirality transfer, which gives the corresponding coupling products with benzylic and allylic stereogenic centers. The wide availability and easy-to-handle nature of arylboronates, the inexpensiveness of the Cu catalyst system, and the high

  （Z）-无环或环状烯丙基磷酸酯与芳基硼酸酯之间的Cu催化的烯丙基-芳基偶联反应具有出色的γ-E-选择性和1,3-抗手性转移，从而产生了具有苄基和烯丙基立体异构中心的相应偶联产物。芳基硼酸酯的广泛可用性和易于处理的性质，Cu催化剂体系的廉价以及高区域选择性和立体选择性是该方案的吸引人的特征。
• Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of Propargylic Ketones
  作者：Andrey Shatskiy、Tove Kivijärvi、Helena Lundberg、Fredrik Tinnis、Hans Adolfsson

  DOI：10.1002/cctc.201500821

  日期：2015.12

  The asymmetric transfer hydrogenation of α,β‐propargyl ketones catalyzed by an in situ formed ruthenium–hydroxyamide complex was explored. The acetylenic alcohols were isolated in good to excellent yields with excellent ee values (typically >90 %) after short reaction times at room temperature.

  探索了原位形成的钌-羟酰胺配合物催化的α，β-炔丙基酮的不对称转移氢化。在室温下短时间反应后，以良好的收率分离出炔醇，并获得优异的ee值（通常> 90％）。