(R)-naphthalen-2-yl 2-((4-methoxyphenylsulfonamido)(phenyl)methyl)acrylate | 1268833-09-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-naphthalen-2-yl 2-((4-methoxyphenylsulfonamido)(phenyl)methyl)acrylate
• 英文别名: naphthalen-2-yl (R)-2-((4-Methoxyphenylsulfonamido)(phenylmethyl))acrylate；naphthalen-2-yl 2-[(R)-[(4-methoxyphenyl)sulfonylamino]-phenylmethyl]prop-2-enoate
• CAS: 1268833-09-5
• 化学式: C₂₇H₂₃NO₅S
• 分子量: 473.549
• InChiKey: DFHXZWWOSYKKCE-SANMLTNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  90.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-萘基丙烯酸酯 、 (E)-N-benzylidene-4-methoxybenzenesulfonamide 在 N-((2S,3R)-3-((2,3-dimethylbutan-2-yl)dimethylsilyloxy)-1-(diphenylphosphino)butan-2-yl)-4-methylbenzenesulfonamide 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以89%的产率得到(R)-naphthalen-2-yl 2-((4-methoxyphenylsulfonamido)(phenyl)methyl)acrylate
  参考文献：
  名称：

  l-Threonine-Derived Novel Bifunctional Phosphine−Sulfonamide Catalyst-Promoted Enantioselective Aza-Morita−Baylis−Hillman Reaction

  摘要：

  A series of novel bifunctional phosphine sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. L-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities.

  DOI：

  10.1021/ol103145g

文献信息

• α-Isocupreine, an Enantiocomplementary Catalyst of β-Isocupreidine
  作者：Yoshito Nakamoto、Fumiya Urabe、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1002/chem.201302665

  日期：2013.9.16

  Complementary chemistry! α‐Isocupreine (α‐ICPN) was synthesized for the first time in one step from quinine by treatment with CF3SO3H (see scheme). This compound serves as an enantiocomplementary catalyst to β‐isocupreidine (β‐ICD) in the Morita–Baylis–Hillman reaction.

  互补化学！通过CF 3 SO 3 H处理，从奎宁一步一步合成了α-异cupreine（α-ICPN）（参见方案）。在Morita-Baylis-Hillman反应中，该化合物可作为β-异cupreidine（β-ICD）的对映体互补催化剂。
• The origin of enantioselectivity in the l-threonine-derived phosphine–sulfonamide catalyzed aza-Morita–Baylis–Hillman reaction: effects of the intramolecular hydrogen bonding
  作者：Richmond Lee、Fangrui Zhong、Bin Zheng、Yuezhong Meng、Yixin Lu、Kuo-Wei Huang

  DOI：10.1039/c3ob40144h

  日期：——

  L-Threonine-derived phosphine–sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita–Baylis–Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N–H⋯O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity.

  研究发现，L-苏氨酸衍生膦磺酰胺 4 是促进对映体选择性杂-莫里塔-贝利斯-希尔曼（MBH）反应的最有效催化剂，能以优异的对映体选择性得到所需的杂-MBH 加合物。为了阐明所观察到的对映体选择性的来源，我们进行了密度泛函理论（DFT）研究。研究发现，磺酰胺基团和烯醇基团之间的分子内 NâHâ¯O 氢键相互作用对于在烯醇加成亚胺和随后的质子转移步骤中诱导高度的立体化学控制至关重要，从而产生了具有优异对映选择性的氮杂-MBH 反应。