(S)-diethyl (4-phenylbut-3-yn-2-yl) phosphate | 1324010-94-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (S)-diethyl (4-phenylbut-3-yn-2-yl) phosphate
• 英文别名: diethyl [(2S)-4-phenylbut-3-yn-2-yl] phosphate
• CAS: 1324010-94-7
• 化学式: C₁₄H₁₉O₄P
• 分子量: 282.276
• InChiKey: JURXOGFWWQNPFF-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane 、 (S)-diethyl (4-phenylbut-3-yn-2-yl) phosphate 在 ICyCuCl 、 lithium tert-butoxide 作用下， 以 1,4-二氧六环 、 正戊烷 为溶剂， 反应 6.0h， 以146 mg的产率得到(S)-triisopropyl(6-phenylnona-6,7-dien-1-yloxy)silane
  参考文献：
  名称：

  Asymmetric Synthesis of Trisubstituted Allenes: Copper-Catalyzed Alkylation and Arylation of Propargylic Phosphates

  摘要：

  Asymmetric synthesis of trisubstituted allenes is accomplished by copper-catalyzed alkylation and arylation of propargylic phosphates using organoboron nucleophiles. Excellent chirality transfer and regioselectivity, together with good functional group compatibility, were observed in reactions with both alkyl boranes and arylboronic esters.

  DOI：

  10.1021/ol2031119
• 作为产物：
  描述：

  (S)-4-phenyl-3-butyn-2-ol 、 氯磷酸二乙酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以77%的产率得到(S)-diethyl (4-phenylbut-3-yn-2-yl) phosphate
  参考文献：
  名称：

  铜（I）亲核硅对丙炔基氯化物和磷酸盐的区域和化学选择性单和双加成反应。

  摘要：

  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。

  DOI：

  10.1021/ol301827t

文献信息

• Regio- and Stereospecific Copper-Catalyzed Substitution Reaction of Propargylic Ammonium Salts with Aryl Grignard Reagents
  作者：Manuel Guisán-Ceinos、Victor Martín-Heras、Mariola Tortosa

  DOI：10.1021/jacs.7b05273

  日期：2017.6.28

  We have developed a copper-catalyzed substitution reaction of propargylic ammonium salts with aryl Grignard reagents. The reaction is stereospecific and α-regioselective and proceeds with exceptional functional group tolerance. Conveniently, a stable, inexpensive, and commercially available copper salt is used and no added ligand is required.

  我们已经开发了芳基格氏试剂与炔丙基铵盐的铜催化取代反应。该反应是立体特异性的和α-区域选择性的，并且以优异的官能团耐受性进行。方便地，使用稳定，便宜且可商购的铜盐，并且不需要添加的配体。
• Copper(I)-Catalyzed Regioselective Propargylic Substitution Involving Si–B Bond Activation
  作者：Devendra J. Vyas、Chinmoy K. Hazra、Martin Oestreich

  DOI：10.1021/ol201811d

  日期：2011.8.19

  The silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation allows several gamma-selective propargylic substitutions. The regioselectivity (gamma:alpha ratio) Is strongly dependent on the propargylic leaving group. Chloride Is superior to oxygen leaving groups in linear substrates (gamma:alpha > 99:1), and it is only the phosphate group that also shows promising regiocontrol (gamma:alpha = 90:10). That leaving group produces superb gamma-selectivity (gamma:alpha > 99:1) in alpha-branched propargylic systems, and enantioenriched substrates react with excellent central-to-axial chirality transfer.
• 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。
• Asymmetric Synthesis of Trisubstituted Allenes: Copper-Catalyzed Alkylation and Arylation of Propargylic Phosphates
  作者：Mycah R. Uehling、Samuel T. Marionni、Gojko Lalic

  DOI：10.1021/ol2031119

  日期：2012.1.6

  Asymmetric synthesis of trisubstituted allenes is accomplished by copper-catalyzed alkylation and arylation of propargylic phosphates using organoboron nucleophiles. Excellent chirality transfer and regioselectivity, together with good functional group compatibility, were observed in reactions with both alkyl boranes and arylboronic esters.