Diethyl-(1-methyl-3-phenyl-2-propinyl)phosphat | 76782-76-8

• 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: Diethyl-(1-methyl-3-phenyl-2-propinyl)phosphat
• 英文别名: diethyl 4-phenylbut-3-yn-2-yl phosphate
• CAS: 76782-76-8
• 化学式: C₁₄H₁₉O₄P
• 分子量: 282.276
• InChiKey: JURXOGFWWQNPFF-UHFFFAOYSA-N

物化性质

• 沸点：
  365.1±25.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

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：

  1-苯基-1-三甲基硅氧乙烯 、 Diethyl-(1-methyl-3-phenyl-2-propinyl)phosphat 在 三氯化铁 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以47%的产率得到3-methyl-1,5-diphenylpent-4-yn-1-one
  参考文献：
  名称：

  FeCl₃-Catalyzed Nucleophilic Substitution of Propargylic Acetates with Enoxysilanes

  摘要：

  [Graphics]An efficient FeCl3-catalyzed substitution reaction of propargylic acetates with enoxysilanes under mild conditions to afford corresponding gamma-alkynyl ketones has been developed. The substitution reaction is followed by a TsOH-catalyzed cyclization without purification of the gamma-alkynyl ketone intermediates, offering a straightforward synthetic route to tri- or tetrasubstituted furans.

  DOI：

  10.1021/jo701782g
• 作为产物：
  描述：

  Diethyl-(1-hydroxy-1-methyl-3-phenyl-2-propinyl)phosphonat 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.25h， 生成 Diethyl-(1-methyl-3-phenyl-1,2-propadienyl)phosphat 、 Diethyl-(1-methyl-3-phenyl-2-propinyl)phosphat
  参考文献：
  名称：

  Hammerschmidt, Friedrich; Schneyder, Elisabeth; Zbiral, Erich, Chemische Berichte, 1980, vol. 113, # 12, p. 3891 - 3897

  摘要：

  DOI：

文献信息

• 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(II) Triflate-Catalyzed Nucleophilic Substitution of Propargylic Acetates with Enoxysilanes. A Straightforward Synthetic Route to Polysubstituted Furans
  作者：Zhuang-ping Zhan、Shao-pei Wang、Xu-bin Cai、Hui-juan Liu、Jing-liang Yu、Yuan-yuan Cui

  DOI：10.1002/adsc.200700234

  日期：2007.9.3

  A novel and efficient procedure for the synthesis of γ-alkynyl ketones by the nucleophilic substitution of propargylic acetates with enoxysilanes in the presence of a catalytic amount of Copper(II) triflate, has been developed. The substitution reaction can be followed by a 4-toluenesulfonic acid-catalyzed cyclization without purification of the γ-alkynyl ketone intermediates, offering a straightforward

  已经开发了在催化量的三氟甲磺酸铜（II）存在下通过用环氧硅烷的炔丙基乙酸酯的亲核取代合成γ-炔基酮的新颖而有效的方法。取代反应之后可以进行4-甲苯磺酸催化的环化反应，而无需纯化γ-炔基酮中间体，从而提供了直接的合成路线来制备多取代的呋喃。
• Asymmetric synthesis of α-chiral β-hydroxy allenes: copper-catalyzed γ-selective borylative coupling of vinyl arenes and propargyl phosphates
  作者：Jung Tae Han、Jaesook Yun

  DOI：10.1039/c9cc04165f

  日期：——

  enantioselective coupling of vinyl arenes with bis(pinacolato)diboron (B2pin2) and propargylic phosphates is presented. The protocol affords a facile route to enantioenriched α-branched allenes with a versatile pinacolboronate group at the β-position with high enantioselectivity up to 98 : 2 er. In the presence of a copper catalyst complexed with a chiral bisphosphine ligand, catalytic assembly of α-chiral β-hydroxy

  提出了铜芳烃与双（频哪醇）二硼（B 2 pin 2）和炔丙基磷酸酯的铜催化对映选择性偶联。该方案提供了一种容易的途径，以丰富的对映体选择性高达98：2 er的途径，将对映体富集的α支化烯基在β位置具有一个通用的频哪醇硼酸酯基团，并具有高对映选择性。在与手性双膦配体络合的铜催化剂的存在下，通过将硼烷基烷基铜物质高度选择性地γ-加成至炔丙基底物，然后氧化，完成α-手性β-羟基烯丙基的催化组装。所得丙二烯的催化剂控制的发散环化反应导致简明的对映体富集的二氢吡喃和二氢呋喃环的合成，而没有任何手性纯度的损失。
• One‐Step Synthesis of Cyclobutene‐Annulated Fullerenes through a Cascade Reaction
  作者：Michio Yamada、Yuta Uokawa、Shino Sasaki、Naohiro Iha、Yoshihisa Hashimoto、Yuya Nagasaki、Yutaka Maeda、Mitsuaki Suzuki

  DOI：10.1002/ejoc.202300633

  日期：2023.9.14

  A one-step method was developed to produce cyclobutenofullerenes via the reaction of fullerene C60 with secondary propargylic phosphates. The reaction cascade comprised the 1,3-migration of the propargylic phosphate to form an allene intermediate followed by a formal [2+2] cycloaddition with C60, and the subsequent 1,3-migration and 1,2-elimination of the phosphodiester moiety.

  开发了一种一步法，通过富勒烯 C 60与仲丙炔磷酸酯反应生产环丁烯富勒烯。反应级联包括磷酸炔丙酯的 1,3-迁移形成丙二烯中间体，随后与 C 60进行正式的 [2+2] 环加成，以及随后磷酸二酯的 1,3-迁移和 1,2-消除部分。
• Ir-Catalyzed Substitution of Propargylic-type Esters with Enoxysilanes
  作者：Isamu Matsuda、Ken-ichi Komori、Kenji Itoh

  DOI：10.1021/ja0264089

  日期：2002.8.1

  Propargylic-type acetates react readily with enoxysilanes in the presence of 1 mol % of [Ir(cod)P(OPh)3}2]OTf activated preliminarily with molecular H2 to give beta-alkynyl ketones in high to excellent yields. Substitution at the propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.