3-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl]oxazolidin-2-one | 109428-72-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl]oxazolidin-2-one
• 英文别名: (1'S,2'R,4'S)-3-(bicyclo[2.2.1]hept-5'-ene-2'-carbonyl)-2-oxazolidinone；3-(bicyclo[2.2.1]hept-5-en-2-carbonyl)oxazolidin-2-one；3-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-ene-2-carbonyl]-1,3-oxazolidin-2-one
• CAS: 109428-72-0
• 化学式: C₁₁H₁₃NO₃
• 分子量: 207.229
• InChiKey: STDSCZJTXUQDHF-DJLDLDEBSA-N

物化性质

• 沸点：
  378.9±31.0 °C(Predicted)
• 密度：
  1.353±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl]oxazolidin-2-one 在 palladium on activated charcoal 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 为溶剂， 反应 6.0h， 生成 2-exo-norbornylic acid
  参考文献：
  名称：

  An efficient catalyst for highly enantioselective exo-Diels–Alder reaction between alkenoyl-1,3-oxazolidin-2-ones and cyclopentadiene

  摘要：

  The typically endo-selective Diels-Alder reactions of cyclopentadiene with acryloyl- and (E)-crotonoyl-oxazolidin-2-ones have been studied to find exo-selective catalysts. Whereas bis(oxazoline)-based catalysts promote high degree of endo-selectivity (with high ee), those derived from 2,6-bis[(4'R,5'R)-diphenyl-1',3'-oxazolin-2'-yl]pyridine (pybox) and the triflates of Eu-III La-III and Ce-IV induce different stereo selectivity. Not only the exo products are obtained with Eu-III in more than 50% yield, but the enantioselectivity is excellent (more than 99% ee). The absolute configuration of the previously unknown exo cycloadduct was unambiguously determined. A stereochemical model is proposed for the activated substrate-catalyst complex which suggests that the excellent efficiency of diphenyl-substituted pybox, compared to that of the corresponding 4-phenyl-substituted ligand, is due to the substituent in the 5-position, suitably placed to blind the Re-face of the coordinated reagent. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00201-6
• 作为产物：
  描述：

  环戊二烯 、 3-丙烯酰基-2-唑烷酮 在 1-benzyl-5,5-dimethyl-2-pyridin-2-ylpyrazolidin-3-one 、 (S,S)-2,2'-异亚丙基双(4-苯基-2-恶唑啉) cobalt(II) perchlorate 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 3-[(1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl]oxazolidin-2-one
  参考文献：
  名称：

  助流添加剂：对映选择性催化的第二代控制

  摘要：

  “通量添加剂”的概念，即可以根据配体中的手性信息采用对映体构象的添加剂，在对映选择性 Diels-Alder 和硝酮环加成反应中得到了证明。增材设计是模块化的，可以通过三个步骤访问不同的结构。在这些添加剂的存在下，来自主族和过渡金属的手性路易斯酸显示出对映选择性的增强。

  DOI：

  10.1021/ja064472a

文献信息

• Porous and Robust Lanthanide Metal-Organoboron Frameworks as Water Tolerant Lewis Acid Catalysts
  作者：Yan Liu、Ke Mo、Yong Cui

  DOI：10.1021/ic400598x

  日期：2013.9.16

  number of isolated Lewis acid B(III) and Ln(III) sites on the pore surfaces. The Nd-MOF assisted with sodium dodecylsulfate was found to be highly effective, recyclable, and reusable heterogeneous catalyst for the carbonyl allylation reaction, the Diels–Alder reaction, and the Strecker-type reaction in water. The transformations were cocatalyzed by Nd(III) and B(III) Lewis acids, with activities much

  多孔且坚固的12连接金属-有机骨架（MOF）是通过将四核镧系（Ln）碳酸酯簇与有机硼衍生的三羧酸酯桥联配体连接而构建的。高连接性的Ln-MOF具有出色的热稳定性和水解稳定性，并且在孔表面具有大量的孤立的路易斯酸B（III）和Ln（III）位。发现Nd-MOF辅以十二烷基硫酸钠可用于水中的羰基烯丙基化反应，Diels-Alder反应和Strecker型反应，是高效，可回收和可重复使用的非均相催化剂。Nd（III）和B（III）Lewis酸可共同催化转化，其活性远高于有机硼和镧系元素对应物及其混合物的活性。
• Chiral 2,2′-Binaphthyldiimine–Nickel(II) Complexes as Lewis Acid Catalysts for Enantioselective Diels–Alder Reactions
  作者：Hiroyuki Suga、Akikazu Kakehi、Masashi Mitsuda

  DOI：10.1246/bcsj.77.561

  日期：2004.3

  The preparation and application of a novel class of chiral Lewis acid catalysts based on chiral 2,2′-binaphthyldiimine ligands are described. Among the binaphthyldiimine–metal complexes tested, N,N...

  描述了一类基于手性 2,2'-联萘二亚胺配体的新型手性路易斯酸催化剂的制备和应用。在测试的联萘二亚胺-金属络合物中，N,N...
• Chiral Bidentate (Phosphinophenyl)benzoxazine Ligands in Asymmetric Catalysis
  作者：Gérald H. Bernardinelli、E. Peter Kündig、Peter Meier、Andreas Pfaltz、Karin Radkowski、Nicole Zimmermann、Margareta Neuburger-Zehnder

  DOI：10.1002/1522-2675(20011017)84:10<3233::aid-hlca3233>3.0.co;2-l

  日期：2001.10.17

  zine ligands 2 were applied in asymmetric catalysis. Rhodium and copper complexes catalyzed the hydrosilylation of acetophenone and [4+2] cycloadditions with moderate enantioselectivity. Iridium complexes were used to hyrogenate di-, tri-, and tetrasubstituted alkenes, giving products with moderate to high enantiomer excesses. Enantioselective allylic substitution and Heck reactions catalyzed by [

  新的手性双齿（膦基芳基）苯并恶嗪配体2被应用于不对称催化。铑和铜配合物催化苯乙酮的氢化硅烷化和具有中等对映选择性的 [4+2] 环加成反应。铱配合物用于氢化二、三和四取代的烯烃，得到对映体过量中度至高度的产物。[(膦基芳基)苯并恶嗪]钯配合物催化的对映选择性烯丙基取代和Heck反应具有高对映选择性。结果与用相应的二氢(膦基芳基)恶唑配体获得的结果相似。
• Lewis Acid-Catalyzed Asymmetric Diels&amp;ndash;Alder Reactions Using Chiral Sulfoxide Ligands: Chiral 2-(Arylsulfinylmethyl)-1,3-oxazoline Derivatives
  作者：Kazuhiro Watanabe、Takashi Hirasawa、Kunio Hiroi

  DOI：10.1248/cpb.50.372

  日期：——

  New chiral sulfoxide-1,3-oxazoline ligands have been developed as chiral ligands for Lewis acid-catalyzed asymmetric Diels-Alder reactions. The use of chiral sulfinyl 1,3-oxazoline ligands in copper(II)-catalyzed asymmetric Diels-Alder reactions provided an endo cycloadduct as a major product with moderate enantioselectivity. A rationale is proposed for the mechanism of the asymmetric induction.

  已开发出新的手性亚砜-1,3-恶唑啉配体作为路易斯酸催化的不对称Diels-Alder反应的手性配体。在铜（II）催化的不对称Diels-Alder反应中使用手性亚磺酰基1,3-恶唑啉配体可提供内环加合物作为主要产物，具有中等对映选择性。提出了不对称感应机理的基本原理。
• The Preparation and Utility of Bis(sulfinyl)imidoamidine Ligands for the Copper-Catalyzed Diels−Alder Reaction
  作者：Timothy D. Owens、Andrew J. Souers、Jonathan A. Ellman

  DOI：10.1021/jo020524c

  日期：2003.1.1

  The design and preparation of a novel class of ligands based on the sulfinyl imine functionality is described. In particular, an efficient and modular synthesis of bis(sulfinyl)imidoamidine (siam) ligands is reported. The versatility of the synthetic sequence is demonstrated by the preparation of various analogues to explore the effect of substitution about the ligand framework on catalytic activity

  描述了基于亚磺酰基亚胺官能团的新型配体的设计和制备。特别地，报道了双（亚磺酰基）亚氨基am（siam）配体的有效和模块化的合成。合成序列的多功能性通过制备各种类似物来证明，以探索关于配体骨架的取代对催化活性的影响。siam配体在不对称催化中的效用在Cu（II）催化的Diels-Alder反应中得到了证明，其中报道了一系列N-酰基氧杂唑烷酮二烯亲和体和二烯底物组合的高度对映和非对映选择性反应。特别值得注意的是这些不对称催化剂对涉及具有挑战性和相对不反应性的无环二烯底物的反应的效率。最后，