tert-butyl (S)-[1-(4-methoxyphenyl)-2-nitroethyl]carbamate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: tert-butyl (S)-[1-(4-methoxyphenyl)-2-nitroethyl]carbamate
• 英文别名: (S)-tert-butyl 1-(4-methoxyphenyl)-2-nitroethylcarbamate；tert-butyl [(1S)-1-(4-methoxylphenyl)-2-nitroethyl]carbamate；tert-butyl N-[(1S)-1-(4-methoxyphenyl)-2-nitroethyl]carbamate
• 化学式: C₁₄H₂₀N₂O₅
• 分子量: 296.323
• InChiKey: SLYQIXOPOOKQSY-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  93.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  tert-butyl (4-methoxyphenyl)(phenylsulfonyl)methylcarbamate 在 水 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 tert-butyl (S)-[1-(4-methoxyphenyl)-2-nitroethyl]carbamate
  参考文献：
  名称：

  Chiral ureas and thioureas supported on polystyrene for enantioselective aza-Henry reactions under solvent-free conditions

  摘要：

  手性可回收支持的双功能脲或硫脲在无溶剂条件下促进高对映选择性的无溶剂条件下的氮杂-Henry反应。

  DOI：

  10.1039/c4gc02474e

文献信息

• The Amino Thiourea-Catalyzed Asymmetric Nucleophilic Reactions
  作者：Yoshiji Takemoto、Hideto Miyabe

  DOI：10.2533/chimia.2007.269

  日期：——

  Bifunctional amino thiourea-catalyzed asymmetric additions of several nucleophiles into electron-deficient unsaturated compounds such as nitroolefins, ?,?-unsaturated imides, imines, and azodicarboxylates are described. We discovered that bifunctional thioureas bearing a tertiary amino group significantly accelerated several nucleophilic addition reactions of active methylene compounds to electron-deficient double bonds. In these reactions, a strong hydrogen-bonding ability of the thiourea moiety as well as an appropriate Brønsted basicity of the tertiary amine is crucial for high enantioselectivity. This dual activation of both nucleophiles and electrophiles by the bifunctional thiourea expanded the applicability of the thiourea-catalyzed enantioselective reaction. In addition, these organocatalyzed asymmetric reactions were successfully applied to the concise asymmetric synthesis of natural products and medicinal candidates such as epibatidine, baclofen, and CP-99,994.

  双功能氨基硫脲催化的不对称加成反应将几种亲核试剂加入到电子不足的不饱和化合物中，如硝基烯烃、α，β-不饱和亚酰胺、亚胺和叠氮二羧酸酯。我们发现，含有三级胺基的双功能硫脲显著加速了活性亚甲基化合物与电子不足双键的几种亲核加成反应。在这些反应中，硫脲基团的强氢键能力以及三级胺的适当Brønsted碱性对高对映选择性至关重要。双功能硫脲对亲核试剂和电子亲电试剂的双重活化扩展了硫脲催化的不对称反应的适用范围。此外，这些有机催化的不对称反应成功应用于天然产物和药用候选化合物的简洁不对称合成，如蛙毒碱、氯硝西泮和CP-99,994。
• Enantioselective aza-Henry reaction using cinchona organocatalysts
  作者：Luca Bernardi、Francesco Fini、Raquel P. Herrera、Alfredo Ricci、Valentina Sgarzani

  DOI：10.1016/j.tet.2005.09.076

  日期：2006.1

  The aza-Henry reaction of imines with nitromethane was promoted by cinchona alkaloids and modified cinchona bases to give optically active β-nitroamines. Various N-protected imines were examined as substrates. N-Boc, N-Cbz, and N-Fmoc protected imines gave the best results in terms of chemical yields and enantioselectivities. After a careful screening of a series of chiral bases, very good enantioselectivities

  金鸡纳生物碱和修饰的金鸡纳碱可促进亚胺与硝基甲烷的aza-Henry反应，从而生成光学活性的β-硝胺。检查了各种N-保护的亚胺作为底物。ñ -Boc，ñ -Cbz和ñ -Fmoc保护亚胺的结果最好的化学产率和对映选择性的条款。在仔细筛选一系列手性碱后，使用金鸡纳基硫脲有机催化剂在优化的反应条件下获得了高达94％ee的良好对映选择性。
• Oxazoline-Thiourea as a Bifunctional Organocatalyst: Enantioselective aza-Henry Reactions
  作者：Yu-wei Chang、Jing-jun Yang、Jin-ning Dang、Yue-xia Xue

  DOI：10.1055/s-2007-984916

  日期：——

  Bifunctional oxazoline-thiourea-based organocatalysts were synthesized and applied to the aza-Henry reactions between N-Boc aryl imines and nitromethane in high ee and chemical yields at room temperature.

  合成了基于恶唑啉-硫脲的双功能有机催化剂，并将其应用于 N-Boc 芳基亚胺与硝基甲烷之间的 aza-Henry 反应，在室温下具有高 ee 和化学产率。
• Novel bifunctional thiourea–ammonium salt catalysts derived from amino acids: application to highly enantio- and diastereoselective aza-Henry reaction
  作者：Hong-Yu Wang、Zhuo Chai、Gang Zhao

  DOI：10.1016/j.tet.2013.04.079

  日期：2013.6

  development of new efficient and easily accessible catalysts has been one of the focuses in asymmetric phase-transfer catalysis. In this paper, a novel class of chiral bifunctional thiourea–ammonium phase-transfer catalysts were synthesized from commercially available α-amino acids. The structural modularity of these catalysts permits facile tunings to achieve optimum results, which was demonstrated

  新型高效且易于获得的催化剂的开发一直是不对称相转移催化的重点之一。在本文中，从市场上可买到的α-氨基酸合成了一类新型的手性双官能硫脲-铵相转移催化剂。这些催化剂的结构模块性使其易于调节以获得最佳结果，这在催化氮杂-亨利反应中表现出优异的对映选择性（高达99.5％ee）和非对映选择性（高达> 25：1 dr）得到了证明。
• A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction
  作者：Constantinos Rampalakos、William D. Wulff

  DOI：10.1002/adsc.200800214

  日期：2008.8.4

  A novel bis-thiourea BINAM-based catalyst for the asymmetric aza-Henry reaction has been developed. This catalyst promotes the reaction of N-Boc imines with nitroalkanes to afford beta-nitroamines with good yields and high enantioselectivities. This catalyst has the advantage that it can be prepared in a single step from commercially available materials. A model is proposed for the catalyst action

  已经开发了一种用于不对称氮杂-亨利反应的新型双硫脲 BINAM 基催化剂。这种催化剂促进了 N-Boc 亚胺与硝基烷烃的反应，以提供具有良好收率和高对映选择性的 β-硝基胺。这种催化剂的优点是它可以由市售材料一步制备。提出了一种催化剂作用模型，其中反应的两种组分通过氢键同时活化。不管机理如何，本催化剂的成功证明了双硫脲作为一类有趣的相对未开发的催化剂的潜力。