(4Sp,13Rp)-4-bromo-13-(4,4-dimethyl-2-oxazolin-2-yl)[2.2]paracyclophane | 308366-28-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: (4Sp,13Rp)-4-bromo-13-(4,4-dimethyl-2-oxazolin-2-yl)[2.2]paracyclophane
• 英文别名: 4-bromo-13-(4,4-dimethyloxazolin-2-yl)[2.2]paracyclophane；2-(12-bromo-5-tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaenyl)-4,4-dimethyl-5H-1,3-oxazole
• CAS: 308366-28-1；404589-55-5；770737-11-6
• 化学式: C₂₁H₂₂BrNO
• 分子量: 384.316
• InChiKey: ZDZJVJSKZYICMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4Sp,13Rp)-4-bromo-13-(4,4-dimethyl-2-oxazolin-2-yl)[2.2]paracyclophane 在 盐酸 、 氯化亚砜 、 sodium azide 、 碘 、 magnesium 作用下， 以 四氢呋喃 、 水 、 丙酮 、 甲苯 为溶剂， 反应 67.0h， 生成 4-amino-13-carbomethoxy[2.2]paracyclophane
  参考文献：
  名称：

  Oxazoline Mediated Routes to a Unique Amino-acid, 4-Amino-13-carboxy[2.2]paracyclophane, of Planar Chirality

  摘要：

  Efficient syntheses leading to 4-amino-13-carboxy[2.2]paracyclophane and derivatives are described. Novel oxazolinyl[2.2]paracyclophanes are used as intermediates and the oxazolinyl and amide groups are shown to be strong psi-geminal directing groups. Compounds with potential as catalysts have been made. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00644-x
• 作为产物：
  描述：

  对二甲苯二聚体 在 氯化亚砜 、 溴 、 碘 、 铁粉 、 magnesium 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 乙腈 为溶剂， 反应 56.0h， 生成 (4Sp,13Rp)-4-bromo-13-(4,4-dimethyl-2-oxazolin-2-yl)[2.2]paracyclophane
  参考文献：
  名称：

  Oxazoline Mediated Routes to a Unique Amino-acid, 4-Amino-13-carboxy[2.2]paracyclophane, of Planar Chirality

  摘要：

  Efficient syntheses leading to 4-amino-13-carboxy[2.2]paracyclophane and derivatives are described. Novel oxazolinyl[2.2]paracyclophanes are used as intermediates and the oxazolinyl and amide groups are shown to be strong psi-geminal directing groups. Compounds with potential as catalysts have been made. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00644-x

文献信息

• Regulation of the flexibility of planar chiral [2.2]paracyclophane ligands and its significant impact on enantioselectivity in asymmetric reactions of diethylzinc with carbonyl compounds
  作者：Xun-Wei Wu、Tang-Zhi Zhang、Ke Yuan、Xue-Long Hou

  DOI：10.1016/j.tetasy.2004.06.026

  日期：2004.8

  A series of planar chiral ligands derived from [2.2]paracyclophane were synthesized and applied as catalysts in enantioselective additions of diethylzinc to aldehydes and α,β-unsaturated ketones. When ligand 10 with a dimethyl hydroxymethyl as the substituent was used, the enantioselectivity of the reaction of diethylzinc with aldehydes was much higher than when using ligand 3c with diphenyl hydroxymethyl

  合成了一系列衍生自[2.2]对环环烷的平面手性配体，并将其用作催化剂，将二乙基锌与醛和α，β-不饱和酮进行对映选择性加成。当使用具有二甲基羟甲基作为取代基的配体10时，二乙基锌与醛的反应的对映选择性比使用具有二苯基羟甲基作为取代基的配体3c的对映选择性高得多。当使用羟甲基取代的配体7b时，将二乙基锌1,4-加成到α，β-不饱和酮上时，情况相同，ee为63-83％，而如果使用配体3c，则几乎不提供对映选择性。还研究了平面手性的作用。
• The synthesis of homochiral ligands based on [2.2]paracyclophane
  作者：Andrew Pelter、Baldwin Mootoo、Anderson Maxwell、Alicia Reid

  DOI：10.1016/s0040-4039(01)01808-1

  日期：2001.11

  A new ortho-lithiation of homochiral 4-N,N-diethylamido[2.2]paracyclophane 8 is the key to the production of a wide variety of 4,5-disubstituted homochiral ligands. psi -Geminal bromination of 8 proceeds in high yields and the resulting bromide may be converted into a variety of 4,13-disubstituted ligands. The o-lithiation and psi -geminal reactions can be used sequentially to give 4,5,12-trisubstituted compounds in which two liganding groups have the same geometrical relationship as in 'Phanephos'(TM). Homochiral oxazolines with only planar chirality have been made, one of which has been shown to be an effective catalyst for the Heck reaction. (C) 2001 Elsevier Science Ltd. All rights reserved.