Diethyl 3-(naphthalen-1-yl)prop-2-en-1-yl phosphate | 815610-70-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Diethyl 3-(naphthalen-1-yl)prop-2-en-1-yl phosphate
• 英文别名: diethyl 3-naphthalen-1-ylprop-2-enyl phosphate
• CAS: 815610-70-9
• 化学式: C₁₇H₂₁O₄P
• 分子量: 320.325
• InChiKey: KFHUXOJJWCAIKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  Diethyl 3-(naphthalen-1-yl)prop-2-en-1-yl phosphate 、 1,3-二(叔丁氧基羰基)胍 在 氢氧化铯 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 2,6-二[(4S)-4-苯基-2-恶唑啉基]吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 8.17h， 以69%的产率得到N1,N2-bis(tert-butyloxycarbonyl)-N1-(1-naphth-1-yl-prop-2-enyl)guanidine
  参考文献：
  名称：

  Palladium- or Iridium-Catalyzed Allylic Substitution of Guanidines: Convenient and Direct Modification of Guanidines

  摘要：

  As a convenient and direct functionalization of guanidines, the transition metal-catalyzed allylic substitution of guanidines was studied. The guanidine derivatives bearing two electron-withdrawing substituents acted as reactive nucleophiles in the allylic substitution to give the rnonoallylated products. The double allylic substitution was achieved by using tri-Boc-guanidine bearing three electron-withdrawing substituents as a nucleophile to give the diallylated products. The regiocontrol in the allylic substitution of unsymmetrical allylic substrates has been investigated by employing the palladium or iridium catalysts. The iridium complex of chiral pybox ligand allowed the regio- and enantioselective allylic substitution. Asymmetric double allylic substitution of tri-Boc-guanidine with phosphate bearing the 1-naphthyl group gave the diallylated product with high diastereo-, regio-, and enantioselectivities.

  DOI：

  10.1021/jo802271d

文献信息

• Bidentate Hydroxyalkyl NHC Ligands for the Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Grignard Reagents
  作者：Magaly Magrez、Yann Le Guen、Olivier Baslé、Christophe Crévisy、Marc Mauduit

  DOI：10.1002/chem.201203969

  日期：2013.1.21

  Demonstrating their potential: Bidentate alkoxy NHC ligands have been used in the copper‐catalyzed asymmetric allylic alkylation of allyl phosphates with Grignard reagents (see scheme). The method provides access to tertiary and quaternary chiral centers with high regio‐ and enantioselectivity. The system is also applied to the synthesis of chiral E,E‐dienes, a key structural motif prevalent in natural

  证明其潜力：用格氏试剂在铜催化的烯丙基磷酸的不对称烯丙基烷基化反应中使用了确定的烷氧基NHC配体（参见方案）。该方法可进入具有高区域和对映选择性的三级和四级手性中心。该系统还适用于手性E，E-二烯的合成，手性E，E-二烯是天然产物中普遍存在的关键结构基序。
• Chelating Hydroxyalkyl NHC as Efficient Chiral Ligands for Room-Temperature Copper-Catalyzed Asymmetric Allylic Alkylation
  作者：Christophe Crévisy、Marc Mauduit、Thomas Jennequin、Joanna Wencel-Delord、Diane Rix、Julien Daubignard

  DOI：10.1055/s-0029-1220127

  日期：2010.7

  The application of chiral chelating hydroxy NHC in copper-catalyzed asymmetric allylic alkylation (Cu-AAA) involving various dialkylzincs and allylic phosphate substrates is reported here. From a library of 11 chiral chelating hydroxyalkyl NHC, a fine-tuning has been done to identify the best architectural features enabling to produce the expected γ-adducts in total regioselectivity, good isolated

  本文报道了手性螯合羟基 NHC 在涉及各种二烷基锌和烯丙基磷酸酯底物的铜催化不对称烯丙基烷基化 (Cu-AAA) 中的应用。从 11 种手性螯合羟烷基 NHC 库中，进行了微调以确定最佳结构特征，从而能够在总区域选择性、良好的分离产率和出色的对映选择性（范围从 93% 到 >98 % ee）。
• Regio- and Enantioselective Allylic Substitution with Less Active N- or O-Nucleophiles Catalyzed by Iridium-Complex of Bis(oxazolinyl)pyridine
  作者：Hideto Miyabe、Katsuhiko Moriyama、Yoshiji Takemoto

  DOI：10.1248/cpb.59.714

  日期：——

  The utility of hydroxylamines as nitrogen nucleophiles was investigated in the iridium-catalyzed regio- and enantioselective allylic substitution. Allylic substitution with hydroxylamines proceeded with good enantioselectivities by using the iridium-complex of bis(oxazolinyl)pyridine ligand. The good regio- and enantioselectivities were also achieved in the reaction with alkylamines, p-anisidine, and 4-methoxyphenol.

  研究了羟胺作为氮亲核物在铱催化的区域和对映选择性烯丙基取代中的作用。通过使用双（噁唑啉基）吡啶配体的铱络合物，羟胺的烯丙基取代反应具有良好的对映选择性。在与烷基胺、对甲氧基苯胺和 4-甲氧基苯酚的反应中也实现了良好的区域和对映选择性。
• Phosphinative cyclopropanation of allyl phosphates with lithium phosphides
  作者：Ryo Shintani、Ayase Ohzono、Kentaro Shirota

  DOI：10.1039/d0cc04854b

  日期：——

  A new cyclopropanation reaction of allyl phosphates with lithium phosphides has been developed to give cyclopropylphosphines through the formation of both a C–P bond and a cyclopropane ring at the same time, and high selectivity toward cyclopropanation over allylic substitution has been realized by conducting the reaction in the presence of HMPA.

  已开发出一种新的磷酸烯丙酯与磷化锂的环丙烷化反应，通过同时形成一个C-P键和一个环丙烷环来生成环丙基膦，并且通过进行该反应实现了对环丙烷化的高选择性而不是烯丙基取代在HMPA的情况下。
• Synthesis of chiral oxime ethers based on regio- and enantioselective allylic substitution catalyzed by iridium–pybox complex
  作者：Hideto Miyabe、Akira Matsumura、Kazumasa Yoshida、Yoshiji Takemoto

  DOI：10.1016/j.tet.2009.04.005

  日期：2009.6

  reactive nucleophile in the iridium-catalyzed allylic substitution of unsymmetrical substrates to give the branched oxime ethers. Among several chiral ligands evaluated, the iridium complex of pybox ligand having phenyl group catalyzed the allylic substitution of phosphates with high activity to form the branched oxime ethers with good enantioselectivities.

  肟的氧原子在铱催化的不对称底物的烯丙基取代中充当反应性亲核试剂，得到支链的肟醚。在所评价的几种手性配体中，具有苯基的pybox配体的铱络合物催化具有高活性的磷酸的烯丙基取代，以形成具有良好对映选择性的支链肟醚。