methyl 2-(((tert-butoxycarbonyl)oxy)(3-fluorophenyl)methyl)acrylate | 1316313-15-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 2-(((tert-butoxycarbonyl)oxy)(3-fluorophenyl)methyl)acrylate
• CAS: 1316313-15-1
• 化学式: C₁₆H₁₉FO₅
• 分子量: 310.322
• InChiKey: BJEBXVYNTCZEJV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.55
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl 2-(((tert-butoxycarbonyl)oxy)(3-fluorophenyl)methyl)acrylate 在 calcium fluoride 、 水 、 hydroquinidine (anthraquinone-1,4-diyl) diether 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 60.0h， 以90%的产率得到(S)-(+)-methyl 3-hydroxy-2-methylene-3-(3-fluorophenyl)propanoate
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e
• 作为产物：
  描述：

  3-氟苯甲醛 在 三乙烯二胺 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 2-(((tert-butoxycarbonyl)oxy)(3-fluorophenyl)methyl)acrylate
  参考文献：
  名称：

  膦催化的[3 + 2]森田-贝利斯-希尔曼碳酸盐与异恶唑基烯烃的环化

  摘要：

  已开发出一种膦催化的森田-贝利斯-希尔曼（MBH）碳酸酯与3-甲基-4-硝基-5-苯乙烯基恶唑的碳酸盐环化反应[3 + 2]，以中等至良好的产率提供各种多功能异恶唑，具有中等至优异的非对映选择性。用螺环手性膦作为催化剂，获得高达89％的ee。

  DOI：

  10.1021/acs.joc.0c01948

文献信息

• Asymmetric Allylic Amination of Morita–Baylis–Hillman Adducts with Simple Aromatic Amines by Nucleophilic Amine Catalysis
  作者：Xin Chen、Shuai Zhao、Zhi-Li Chen、Xue Rui、Ming-Mei Gao

  DOI：10.1055/s-0037-1611740

  日期：2019.4

  Asymmetric allylic amination of Morita–Baylis–Hillman (MBH) adducts with simple aromatic amines is successfully realized by nucleophilic amine catalysis. A range of substituted α-methylene-β-arylamino esters is accessed in moderate to high yields (up to 88%) and with excellent enantioselectivities (up to 97% ee). Inorganic fluorides are found to be able to improve the enantioselectivity of the allylic

  Morita-Baylis-Hillman (MBH) 加合物与简单芳香胺的不对称烯丙基胺化是通过亲核胺催化成功实现的。一系列取代的 α-亚甲基-β-芳基氨基酯以中等至高产率（高达 88%）和出色的对映选择性（高达 97% ee）获得。发现无机氟化物能够提高烯丙基胺化反应的对映选择性。吡咯-2-羧酸酯和环状酰亚胺也与该催化体系相容。手性 2,3-二氢喹啉-4-one 衍生物很容易从烯丙基胺化产物中获得。
• Asymmetric synthesis of multifunctional aryl allyl ethers by nucleophilic catalysis
  作者：Shuai Zhao、Lei Jin、Zhi-Li Chen、Xue Rui、Jia-Yi He、Ran Xia、Ke Chen、Xiang-Xiang Chen、Zi-Jian Yin、Xin Chen

  DOI：10.1039/c9ra00155g

  日期：——

  Asymmetric allylic substitution of Morita–Baylis–Hillman (MBH) carbonates with less-nucleophilic phenols mediated by nucleophilic amine catalysis was successfully developed. A variety of substituted aryl allyl ethers were afforded with moderate to high yields with excellent enantioselectivities. The chiral MBH alcohol could be easily accessed from the corresponding aryl allyl ether.

  成功开发了由亲核胺催化介导的低亲核酚类对 Morita-Baylis-Hillman (MBH) 碳酸酯的不对称烯丙基取代。以中等至高产率和优异的对映选择性提供了多种取代的芳基烯丙基醚。手性 MBH 醇可以很容易地从相应的芳基烯丙基醚中获得。
• Organocatalytic Enantioselective Allylic Etherification of Morita–Baylis–Hillman Carbonates and Silanols
  作者：Hui-Li Liu、Ming-Sheng Xie、Gui-Rong Qu、Hai-Ming Guo

  DOI：10.1021/acs.joc.6b01931

  日期：2016.10.21

  The organocatalytic asymmetric allylic etherification reaction of Morita–Baylis–Hillman carbonates and silanols was reported for the first time. With modified cinchona alkaloid (DHQD)2PYR as the catalyst, a series of aromatic, heterocyclic, or aliphatic Morita–Baylis–Hillman carbonates (25 examples) worked well with triphenylsilanol, affording the corresponding products in moderate to good yields (up

  首次报道了森田-贝利斯-希尔曼碳酸盐和硅烷醇的有机催化不对称烯丙基醚化反应。以修饰的金鸡纳生物碱（DHQD）2 PYR为催化剂，一系列芳族，杂环或脂肪族Morita-Baylis-Hillman碳酸盐（25个实例）与三苯基硅烷醇效果很好，从而提供了中等至良好收率的相应产品（高达98 ％），高区域选择性（> 20：1）和良好的对映选择性（最高92％）。当使用二甲基苯基硅烷醇作为亲核试剂时，以60％的收率和87％的ee获得产物。
• Asymmetric Phosphine-Catalyzed [4+1] Annulations of <i>o</i> -Quinone Methides with MBH Carbonates
  作者：Tao Zhou、Tong Xia、Zhenli Liu、Lu Liu、Junliang Zhang

  DOI：10.1002/adsc.201801152

  日期：2018.12.3

  dihydrobenzofuran units are frequently present in molecules with significant biological and pharmaceutical activities. Herein, we present the first enantioselective formal [4+1] annulation of Morita‐Baylis‐Hillman carbonates with o‐quinone methides (o‐QMs) catalyzed by a newly designed chiral phosphine catalyst. Under the mild and eco‐friendly conditions, a wide range of polysubstituted dihydrobenzofurans were

  手性二氢苯并呋喃单元经常存在于具有重要生物学和药学活性的分子中。在本文中，我们介绍了新设计的手性膦催化剂催化的森田贝利斯-希尔曼碳酸盐与邻醌甲基化物（o- QMs）的首次对映选择性形式[4 + 1]环化。在温和和生态友好的条件下，以良好的收率和优异的对映选择性获得了多种多取代的二氢苯并呋喃。
• Enantioselective Synthesis of Carbocyclic Nucleosides via Asymmetric [3 + 2] Annulation of α-Purine-Substituted Acrylates with MBH Carbonates
  作者：Ke-Xin Huang、Ming-Sheng Xie、Qi-Ying Zhang、Gui-Rong Qu、Hai-Ming Guo

  DOI：10.1021/acs.orglett.7b03625

  日期：2018.1.19

  An efficient route to chiral carbocyclic nucleoside analogues containing a quaternary stereocenter and a C═C double bond has been established via a highly enantioselective [3 + 2] annulation of Morita–Baylis–Hillman (MBH) carbonates with α-purine-substituted acrylates. With 20 mol % (S)-SITCP as the catalyst, various chiral carbocyclic nucleoside analogues with a quaternary stereocenter and a C═C double

  通过Morita-Baylis-Hillman（MBH）碳酸盐与α-嘌呤取代的丙烯酸酯的高度对映选择性[3 + 2]环化，已经建立了一种有效的途径来制备包含季立体中心和C═C双键的手性碳环核苷酸类似物。以20 mol％（S）-SITCP为催化剂，可以高收率（高达92％）和良好的非对映选择性（高达10：1 dr ）和极好的对映选择性（ee高达96％）。此外，将相应的产物进行各种转化以提供有趣的和潜在有用的手性碳环核苷。