tert-butyl (2-methoxybenzylidene)carbamate | 957201-90-0

• 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 (2-methoxybenzylidene)carbamate
• 英文别名: o-methoxybenzaldehyde N-(tert-butoxycarbonyl)imine；tert-butyl N-[(2-methoxyphenyl)methylidene]carbamate
• CAS: 957201-90-0
• 化学式: C₁₃H₁₇NO₃
• 分子量: 235.283
• InChiKey: YXWLGSNPUIHAGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl (2-methoxybenzylidene)carbamate 、 2-氰基环戊酮 在 erbium triisopropoxide 、 (S)-N-(2-hydroxyphenyl)-2-(2-hydroxybenzoylamino)-3-methylbutylamide 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以99%的产率得到(S)-2-(((S)-tert-butoxycarbonylamino)(2-methoxyphenyl)methyl)-2-cyanocyclopentanone
  参考文献：
  名称：

  Linking Structural Dynamics and Functional Diversity in Asymmetric Catalysis

  摘要：

  Proteins, the functional molecules in biological systems, are sophisticated chemical devices that have evolved over billions of years. Their function is intimately related to their three-dimensional structure and elegantly regulated by conformational changes through allosteric regulators and a number of reversible or unidirectional post-translational modifications. This functional diversification in response to external stimuli allows for an orderly and timely progression of intra- and extracellular events. In contrast, enantioselective catalysts generally exhibit limited conformational flexibility and thereby exert a single specific function. Exploiting the features of conformationally flexible asymmetric ligands and the variable coordination patterns of rare earth metals, we demonstrate dynamic structural and functional changes of a catalyst in asymmetric catalysis, leading to two distinct reaction outcomes in a single flask.

  DOI：

  10.1021/ja900084k
• 作为产物：
  描述：

  氨基甲酸叔丁酯 在 甲酸 、 potassium carbonate 、 sodium sulfate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 63.0h， 生成 tert-butyl (2-methoxybenzylidene)carbamate
  参考文献：
  名称：

  非C 2对称的前酚配体的开发。N- Boc亚胺的不对称乙烯基化

  摘要：

  本文报道了新一代的非C 2-对称的ProPhenol配体的开发和应用。ProPhenol配体的合理设计为N- Boc亚胺通过氢化锆的首次催化和不对称乙烯基化铺平了道路，从而以极高的收率和对映选择性产生了有价值的烯丙基胺。通过开发最短的报道的选择性5-羟色胺再摄取抑制剂（SSRI）（-）-多巴西汀的不对称合成证明了该方法的实用性。

  DOI：

  10.1021/acs.orglett.5b01755

文献信息

• Modular Bifunctional Chiral Thioureas as Versatile Organocatalysts for Highly Enantioselective Aza-Henry Reaction and Michael Addition
  作者：Hua Li、Xu Zhang、Xin Shi、Nan Ji、Wei He、Shengyong Zhang、Bangle Zhang

  DOI：10.1002/adsc.201200144

  日期：2012.8.13

  A series of new modular bifunctional chiral thiourea organocatalysts were synthesized from natural Cinchona alkaloids and amino acids, and their performance in the aza-Henry reaction of nitroalkanes to imines, the Michael addition of acetylacetone to nitroolefins and the Michael addition of acetone to nitroolefins was investigated. Under the mild conditions, the important building blocks β-nitro amines

  由天然金鸡纳生物碱和氨基酸合成了一系列新型的模块式双功能手性硫脲有机催化剂，研究了它们在硝基烷烃向亚胺的氮杂-亨利反应，乙酰丙酮到硝基烯烃的迈克尔加成反应以及丙酮到硝基烯烃的迈克尔加成反应中的性能。 。在温和的条件下，可以以高收率（高达95％），出色的对映选择性（高达99％ee）和非对映选择性（高达17：1）获得重要的构建基β-硝基胺和γ-硝基羰基化合物。。
• A chiral organic base catalyst with halogen-bonding-donor functionality: asymmetric Mannich reactions of malononitrile with <i>N</i>-Boc aldimines and ketimines
  作者：Satoru Kuwano、Takumi Suzuki、Yusei Hosaka、Takayoshi Arai

  DOI：10.1039/c8cc00865e

  日期：——

  A chiral organic base catalyst with halogen-bonding-donor functionality has been developed. This quinidine-derived acid/base catalyst smoothly promoted the asymmetric Mannich reaction of malononitrile and various N-Boc imines with up to 98% ee. The cooperative interaction with both substrates was responsible for the high activity that allowed a reduction of the catalyst amount to 0.5 mol%.

  已经开发了具有卤素键合给体官能度的手性有机碱催化剂。这种由奎尼丁衍生的酸/碱催化剂顺利地促进了丙二腈和各种N- Boc亚胺的不对称曼尼希反应，ee高达98％。与两种底物的协同相互作用是高活性的原因，该高活性使催化剂的量减少到0.5mol％。
• Direct Asymmetric Vinylogous and Bisvinylogous Mannich-Type Reaction Catalyzed by a Copper(I) Complex
  作者：Hai-Jun Zhang、Chang-Yun Shi、Feng Zhong、Liang Yin

  DOI：10.1021/jacs.6b13042

  日期：2017.2.15

  A direct catalytic asymmetric vinylogous Mannich-type reaction has been disclosed in good yield, excellent regio-, diastereo- and enantioselectivity. The key to control the regioselectivity is the combination of a bulky N-acylpyrazole and a bulky bisphosphine ligand. The catalytic system was extended to a bisvinylogous Mannich-type reaction by changing the ligand. The synthetic utility of the vinylogous

  已经公开了一种直接催化不对称乙烯基曼尼希型反应，其产率高，具有出色的区域选择性、非对映选择性和对映选择性。控制区域选择性的关键是庞大的 N-酰基吡唑和庞大的双膦配体的组合。通过改变配体，催化体系扩展到双乙烯基曼尼希型反应。几种转化证明了乙烯基产物的合成效用。
• 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。
• Direct Catalytic Asymmetric Mannich Reactions for the Construction of Quaternary Carbon Stereocenters
  作者：Barry M. Trost、Tanguy Saget、Chao-I (Joey) Hung

  DOI：10.1021/jacs.6b01187

  日期：2016.3.23

  Mannich reaction using α-branched ketones as nucleophilic partners for the direct enantio- and diastereoselective construction of quaternary carbon stereocenters. The reaction can be run on a gram-scale with a low catalyst loading without impacting its efficiency. Moreover, the Mannich adducts can be further elaborated with complete diastereocontrol to access molecules possessing complex stereotriads.

  在此，我们报告了使用 α-支化酮作为亲核伙伴的 Zn-ProPhenol 催化的曼尼希反应，用于直接对映选择性和非对映选择性构建季碳立体中心。该反应可以以克级规模进行，催化剂负载量低，而不会影响其效率。此外，曼尼希加合物可以通过完全非对映控制进一步细化，以获取具有复杂立体三联体的分子。