(R,E)-4-(naphthalen-2-yl)but-3-en-2-yl pivalate | 1613507-04-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R,E)-4-(naphthalen-2-yl)but-3-en-2-yl pivalate
• CAS: 1613507-04-2
• 化学式: C₁₉H₂₂O₂
• 分子量: 282.382
• InChiKey: QPXMHRXERNWBMJ-ATWMFIQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-[4,6-Bis(3-cyanophenyl)-1,3,5,2,4,6-trioxatriborinan-2-yl]benzonitrile 、 (R,E)-4-(naphthalen-2-yl)but-3-en-2-yl pivalate 在 bis(1,5-cyclooctadiene)nickel (0) 、 sodium methylate 、 苄基二苯膦 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以77%的产率得到(S,E)-3-(4-(naphthalen-2-yl)but-3-en-2-yl)benzonitrile
  参考文献：
  名称：

  Enantiospecific, Nickel-Catalyzed Cross-Couplings of Allylic Pivalates and Arylboroxines

  摘要：

  We have developed an enantiospecific, nickel-catalyzed cross-coupling of unsymmetric 1,3-disubstituted allylic pivalates with arylboroxines. The success of this reaction relies on the use of BnPPh2 as a supporting ligand for the nickel(0) catalyst and NaOMe as a base. This method shows excellent functional group tolerance and broad scope in both the allylic pivalate and arylboroxine, enabling the preparation of 1,3-diaryl allylic products in high yields with excellent levels of regioselectivity and stereochemical fidelity.

  DOI：

  10.1021/ol5016724
• 作为产物：
  描述：

  (E)-4-(naphthalene-2-yl)but-3-en-2-one 在 4-二甲氨基吡啶 、 三乙胺 、 (S)-tetrahydro-1-butyl-3,3-diphenyl-1H,3H-pyrrolo{2,1-c}{1,3,2}oxazaborole 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 39.25h， 生成 (R,E)-4-(naphthalen-2-yl)but-3-en-2-yl pivalate
  参考文献：
  名称：

  Enantiospecific, Nickel-Catalyzed Cross-Couplings of Allylic Pivalates and Arylboroxines

  摘要：

  We have developed an enantiospecific, nickel-catalyzed cross-coupling of unsymmetric 1,3-disubstituted allylic pivalates with arylboroxines. The success of this reaction relies on the use of BnPPh2 as a supporting ligand for the nickel(0) catalyst and NaOMe as a base. This method shows excellent functional group tolerance and broad scope in both the allylic pivalate and arylboroxine, enabling the preparation of 1,3-diaryl allylic products in high yields with excellent levels of regioselectivity and stereochemical fidelity.

  DOI：

  10.1021/ol5016724

文献信息

• Accessing Both Retention and Inversion Pathways in Stereospecific, Nickel-Catalyzed Miyaura Borylations of Allylic Pivalates
  作者：Qi Zhou、Harathi D. Srinivas、Songnan Zhang、Mary P. Watson

  DOI：10.1021/jacs.6b07396

  日期：2016.9.14

  enable access to either enantiomer of allylboronate product from a single enantiomer of readily prepared allylic pivalate substrate. Excellent functional group tolerance, yields, regioselectivities, and stereochemical fidelities are observed. The stereochemical switch from stereoretention to stereoinversion largely depends upon solvent and can be explained by competitive pathways for the oxidative

  我们开发了一种立体有择的、镍催化的烯丙基新戊酸酯的 Miyaura 硼酸化，它提供了高度对映体富集的 α-立体异构 γ-芳基烯丙基硼酸酯，具有良好的产率和区域选择性。我们的互补条件集能够从易于制备的烯丙基新戊酸酯底物的单个对映体中获得烯丙基硼酸酯产物的任一对映体。观察到优异的官能团耐受性、产率、区域选择性和立体化学保真度。从立体保留到立体转化的立体化学转换很大程度上取决于溶剂，可以通过氧化加成步骤的竞争途径来解释。