(R)-1-(4-chlorophenyl)-4-methyl-4-nitro-3-phenylpentan-1-one

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (R)-1-(4-chlorophenyl)-4-methyl-4-nitro-3-phenylpentan-1-one
• 英文别名: (3R)-1-(4-chlorophenyl)-4-methyl-4-nitro-3-phenylpentan-1-one
• 化学式: C₁₈H₁₈ClNO₃
• 分子量: 331.799
• InChiKey: PIQLCRWTKLXEAY-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-硝基丙烷 、 4'-chlorochalcone 在 2Br^(1-)*C₈₆H₅₆F₂₆N₂⁽²⁺⁾ 、 potassium carbonate 作用下， 以 甲苯 为溶剂， 以92%的产率得到(R)-1-(4-chlorophenyl)-4-methyl-4-nitro-3-phenylpentan-1-one
  参考文献：
  名称：

  通过调节相转移催化剂的构象柔性来逆转对映选择性

  摘要：

  朝着完美的不对称催化方向发展：当将二元醇衍生的N螺环季铵盐用作向烷烃及其类似物共轭添加硝基烷烃的相转移催化剂时，观察到了令人感兴趣的对映选择性逆转。已经设计并合成了新型手性催化剂（参见结构）。

  DOI：

  10.1002/anie.200906814

文献信息

• Enantioselective Michael Addition of 2-Nitropropane to Substituted Chalcones and Chalcone Analogues Catalyzed by Chiral Crown Ethers Incorporating an α-D-Glucose or an α-D-Mannose Unit
  作者：Attila Mako、Zsolt Rapi、Laszlo Drahos、Aron Szollosy、Gyorgy Keglevich、Peter Bako

  DOI：10.2174/157017810791824865

  日期：2010.9.1

  The chiral monoaza-15-crown-5 lariat ethers annellated to methyl-4,6-O-benzylidene-α-D-glucopyranoside- (1) or – mannopyranoside (2) used as phase transfer catalysts in the Michael addition of 2-nitropropane to substituted chalcones and chalcone analogues resulted in a significant asymmetric induction. The type of substituent on the chalcone molecule was found to have a significant influence on both the chemical yield and the enantioselectivity of the reaction: 24 novel chiral Michael adducts were prepared in 14-68% ee. These ee values were somewhat lower than that experienced in the case of the unsubstituted chalcone (85% ee). In the series of chalcone analogues, the 1-naphthyl Michael adduct was formed in 87% ee. Using glucose-based crown ether 1, formation of the (+)-enantiomers was preferred, while applying mannose-based 2 as the catalyst, the (-)-enantiomers were in excess.

  在含取代基查尔酮和查尔酮类似物的迈克尔加成反应中，使用手性单氮-15-冠-5套索醚作为相转移催化剂，该套索醚与甲基-4,6-O-苄叉-α-D-吡喃葡萄糖苷（1）或-吡喃甘露糖苷（2）并环，产生了显著的不对称诱导效应。研究发现，查尔酮分子上的取代基类型对反应的化学产率和立体选择性均有显著影响：合成了24种新型手性迈克尔加成产物，其对映体过量值为14-68%。这些对映体过量值略低于无取代基查尔酮的情况（85% ee）。在查尔酮类似物系列中，1-萘基迈克尔加成产物形成于87% ee。使用基于葡萄糖的冠醚1时，优先形成（+）-对映体，而使用基于甘露糖的2作为催化剂时，（-）-对映体过量。
• Nanocrystalline MgO for Asymmetric Henry and Michael Reactions
  作者：Boyapati M. Choudary、Kalluri V. S. Ranganath、Ujjwal Pal、Mannepalli L. Kantam、Bojja Sreedhar

  DOI：10.1021/ja0440248

  日期：2005.9.28

  groups of (S)-(-)-binol and the -OH groups of MgO are essential for the induction of enantioselectivity. Further, to prove the above hypothesis, we have successfully carried out another reaction, asymmetric Michael reaction (AM) with nanocrystalline MgO. The reusable and suitably aligned nanocrystalline MgO-catalyzed AH and AM reactions afforded chiral products with comparable ee's to that of the homogeneous

  具有三维结构和确定的尺寸和形状的纳米材料被认为是与前手性基底正确对齐的合适候选材料，用于单向引入反应物质以诱导不对称中心。我们在此报告了一种真正可回收的多相催化剂纳米晶氧化镁的设计和开发，用于不对称亨利反应 (AH) 以首次提供具有优异收率和良好对映选择性 (ee's) 的手性硝基醇。布朗斯台德羟基是 ee 的唯一贡献者，同时它们增加了 AH 的活性。结果表明，(S)-(-)-binol 的 -OH 基团和 MgO 的 -OH 基团之间的氢键相互作用对于诱导对映选择性至关重要。进一步证明上述假设，我们已经成功地进行了另一个反应，即与纳米晶 MgO 的不对称迈克尔反应 (AM)。可重复使用和适当排列的纳米晶 MgO 催化的 AH 和 AM 反应提供了手性产物，其 ee 与均相系统的 ee 相当。
• Enantioselective Michael reaction of 2-nitropropane with substituted chalcones catalysed by chiral azacrown ethers derived from α-d-glucose
  作者：Tibor Bakó、Péter Bakó、Áron Szöllõsy、Mátyás Czugler、György Keglevich、László Tõke

  DOI：10.1016/s0957-4166(02)00068-x

  日期：2002.2

  The chiral monoaza-15-crown-5 lariat ethers anellated to methyl-4,6-O-benzylidene-alpha-D-glucopyranoside 1a-c showed significant asymmetric induction as phase transfer catalysts in the Michael addition of 2-nitropropane to substituted chalcones. Among the catalysts bearing different side arms at the nitrogen atom, the compound with a phosphinoxidoalkyl side chain 1c proved to be the most effective (max. 78% e.e.). The type of substituent on the chalcone was found to have a very significant influence on both the chemical yield and the enantioselectivity of the reaction. The absolute configuration of the Michael adducts 3b and 3i was determined by chemical methods, while that of 3d was assigned by X-ray crystal structure determination. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Reversal of Enantioselectivity by Tuning the Conformational Flexibility of Phase-Transfer Catalysts
  作者：Ming-Qing Hua、Han-Feng Cui、Lian Wang、Jing Nie、Jun-An Ma

  DOI：10.1002/anie.200906814

  日期：2010.4.1

  Towards perfect asymmetric catalysis: When binol‐derived N‐spiro quaternary ammonium salts were used as phase‐transfer catalysts in the conjugate addition of nitroalkanes to chalcones and its analogues, an intriguing reversal of enantioselectivity was observed. Novel chiral catalysts have been designed and synthesized (see structure).

  朝着完美的不对称催化方向发展：当将二元醇衍生的N螺环季铵盐用作向烷烃及其类似物共轭添加硝基烷烃的相转移催化剂时，观察到了令人感兴趣的对映选择性逆转。已经设计并合成了新型手性催化剂（参见结构）。