(E)-4-methoxy-N-((E)-3-phenylallylidene)benzenesulfonamide | 861145-33-7

• 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: (E)-4-methoxy-N-((E)-3-phenylallylidene)benzenesulfonamide
• 英文别名: (NE)-4-methoxy-N-[(E)-3-phenylprop-2-enylidene]benzenesulfonamide
• CAS: 861145-33-7
• 化学式: C₁₆H₁₅NO₃S
• 分子量: 301.366
• InChiKey: NXSSFQNSQMDACW-WUSSVBECSA-N

物化性质

• 熔点：
  125-190 °C(Solv: toluene (108-88-3))
• 沸点：
  477.6±55.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  64.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  反式-4-氧基-2-丁烯酸乙酯 、 (E)-4-methoxy-N-((E)-3-phenylallylidene)benzenesulfonamide 在 chiral N-heterocyclic carbene 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 23.0h， 以90%的产率得到ethyl 2-((3S,4S)-1-(4-methoxyphenylsulfonyl)-2-oxo-4-phenyl-1,2,3,4-tetrahydropyridin-3-yl)acetate
  参考文献：
  名称：

  Highly Enantioselective Azadiene Diels−Alder Reactions Catalyzed by Chiral N-Heterocyclic Carbenes

  摘要：

  Highly enantioselective, N-heterocyclic carbene (NHC)-catalyzed aza-Diels-Alder reactions are described. A novel chiral triazolium salt based on the cis-1,2-aminoindanol platform serves as an efficient precatalyst for the NHC-catalyzed redox generation of enolate dienophiles that undergo LUMOdiene-controlled Diels-Alder reactions with N-sulfonyl-alpha,beta-unsaturated imines in good yields and with exceptional diastereo- and enantioselectivities (>99% ee). In contrast to uncatalyzed variants, this organocatalytic process proceeds at room temperature without stoichiometric reagents, producing synthetically valuable, enantiomerically pure cis-3,4-disubstituted dihydropyridinone products.

  DOI：

  10.1021/ja062707c
• 作为产物：
  描述：

  (E)-cinnamaldehyde dimethylacetal 、 对甲氧基苯磺酰胺 反应 0.5h， 生成 (E)-4-methoxy-N-((E)-3-phenylallylidene)benzenesulfonamide
  参考文献：
  名称：

  Catalytic Synthesis of γ-Lactams via Direct Annulations of Enals and N-Sulfonylimines

  摘要：

  Cinnamaldehydes and N-sulfonylimines undergo direct annulations to cis-disubstituted gamma-lactams via the intermediacy of catalytically generated homoenolates. Critical to the success of this process was overcoming inhibition of the N-heterocyclic carbene catalyst by the electrophilic imines. The overall process proceeds with good yields and diastereoselectivites and requires no stoichiometric reagents or additives.

  DOI：

  10.1021/ol051234w

文献信息

• Chiral Copper Complexes of Phosphino Sulfenyl Ferrocenes as Efficient Catalysts for Enantioselective Formal Aza Diels−Alder Reactions of <i>N</i>-Sulfonyl Imines
  作者：Olga García Mancheño、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1021/ja038494y

  日期：2004.1.1

  catalytic amount of silver perchlorate, copper(I) bromide complexes of planar chiral 1-phosphino-2-sulfenylferrocenes behave as very efficient chiral Lewis acids catalysts in the formal Aza Diels-Alder reaction of N-arylsulfonyl aldimines with electron-rich dienes (Danishefsky's and related dienes). Mixing of equimolar amounts of the readily available enantiopure ferrocenyl P,S-bidentate ligand and CuBr quantitatively

  在催化量的高氯酸银存在下，平面手性 1-膦基-2-硫基二茂铁的溴化铜（I）络合物在 N-芳基磺酰醛亚胺与电子的正式 Aza Diels-Alder 反应中充当非常有效的手性路易斯酸催化剂。 - 丰富的二烯（Danishefsky's 和相关的二烯）。等摩尔量的容易获得的对映体纯二茂铁基 P，S-二齿配体和 CuBr 的混合定量提供了作为空气稳定固体的预催化剂 Cu 络合物。这种催化不对称过程具有广泛的结构范围：已成功使用芳香族、α、β-不饱和甚至烯醇化脂肪族醛的醛亚胺。相应的 2,3-二氢-4-吡啶酮以良好的产率 (57-90%) 和均匀的高对映选择性 (82-97% ee) 获得。
• Synthesis of an <i>N</i>-Mesityl Substituted Chiral Imidazolium Salt for NHC-Catalyzed Reactions
  作者：Justin R. Struble、Juthanat Kaeobamrung、Jeffrey W. Bode

  DOI：10.1021/ol800006m

  日期：2008.3.1

  A new synthetic approach to chiral imidazolium salts makes possible the first synthesis of an N-mesityl substituted, aminoindanol-derived N-heterocyclic carbene precursor, 1.ClO4. The successful synthesis allows the first direct comparison of otherwise identical imidazolium and triazolium precursors across a number of NHC-catalyzed processes. These studies confirm striking differences in reactivity

  一种新的手性咪唑鎓盐合成方法，使得首次合成N-间苯二甲酰基取代的氨基茚满醇衍生的N-杂环卡宾前体1.ClO4成为可能。成功的合成方法可以在许多NHC催化过程中首次直接比较在其他方面相同的咪唑鎓和三唑鎓前体。这些研究证实了这两类药物在反应性和机理上的显着差异。
• Formal Synthesis of (±)-Clausenamide by NHC-Catalyzed γ-Lactam Formation
  作者：Jeffrey W. Bode、Ming He、Michael Rommel

  DOI：10.3987/com-12-s(n)128

  日期：——

  (+/-)-Clausenamide is a biologically active gamma-lactam isolated as a racemic mixture from Clausena lansium. Reported medicinal properties include hepatoprotective effects as well as neuroprotective and nootropic activity. In order to improve synthetic access to this molecule and its analogues, and to devise a route amenable to asymmetric catalysis, we have developed a new formal synthesis of (+/-)-clausenamide based on an N-heterocyclic carbene (NHC) catalyzed annulation of cinnamaldehyde and an unsaturated imine. The key gamma-lactam forming annulation proceeds at room temperature in good yield and excellent diastereoselectivity. Preliminary efforts towards an enantioselective variant are also reported.

  (±)-Clausenamide是一种具有生物活性的γ-内酰胺，作为消旋混合物从Clausena lansium中分离得到。据报道，它具有保肝作用以及神经营养和促智活性。为了提高合成通向该分子及其类似物的可进入性，并设计一条适用于不对称催化的路线，我们开发了一种新的(±)-clausenamide的正式合成方法，基于N-杂环卡宾（NHC）催化的肉桂醛和不饱和亚胺的环化反应。关键的γ-内酰胺形成环化反应在室温下以良好产率和出色的非对映选择性进行。初步努力实现对映选择性变体的结果也已报告。
• ENANTIOSELECTIVE REACTIONS CATALYZED BY CHIRAL TRIAZOLIUM SALTS
  申请人：Bode Jeffrey

  公开号：US20100210452A1

  公开（公告）日：2010-08-19

  This invention provides a convenient method for converting imines and other electrophiles into heterocyclic ring systems. The process does not require the use of metallic reagents, and is catalyzed by an organic heterocyclic carbene catalyst. Accordingly, it produces the desired compounds without the concomitant production of a large volume of metallic waste. Chiral heterocyclic carbene catalysts of the invention and methods of using these catalysts produce chiral heterocycles in high enantiomeric and diastereomeric excess.

  本发明提供了一种将亚胺和其他亲电试剂转化为杂环环系统的方便方法。该过程不需要使用金属试剂，而是由有机杂环卡宾催化剂催化。因此，它可产生所需化合物而不伴随大量金属废物的产生。本发明的手性杂环卡宾催化剂及其使用方法可产生高对映选择性和立体异构选择性的手性杂环。
• WO2007/124494
  申请人：——

  公开号：——

  公开（公告）日：——