(+)-ethyl exo-3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate | 946431-97-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+)-ethyl exo-3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate
• 英文别名: (1R,2S,3S,4S)-ethyl 3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate；ethyl (1R,2S,3S,4S)-3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 946431-97-6
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: PTOWCTCRIJFDMK-KATARQTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-ethyl exo-3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 (5S,6S)-bis(hydroxymethyl)bicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  Conformational diagnosis of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate based on the stereochemical outcomes of representative reactions as compared with those of its 4,5-O-isopropylidene derivatives and on a dichroic exciton chirality method

  摘要：

  In order to gain more insight into the conformation of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate (1) experimentally, some appropriate reactions of 1 and its derivative (S,S)-3, which bears isopropylidene protecting groups, have been executed. The stereochemical outcomes of such reactions as the Diels-Alder reaction, osmium tetraoxide-catalyzed hydroxylation, conjugate addition with amines, and cyclopropanation with phosphonium ylides point to a rigid conformation (1A) in which the vicinal TBDMSO groups, the most bulky substituents, are arranged in an anti relationship, and, therefore, the enoate groups are forced to be gauche each other. A dichroic exciton chirality study has also provided clear-cut evidence for this rigid conformation.

  DOI：

  10.1021/jo00075a024
• 作为产物：
  描述：

  Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate 在 sodium periodate 、 四丁基氟化铵 、 氯化二乙基铝 、 碳酸氢钠 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 (+)-ethyl exo-3-formylbicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  Conformational diagnosis of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate based on the stereochemical outcomes of representative reactions as compared with those of its 4,5-O-isopropylidene derivatives and on a dichroic exciton chirality method

  摘要：

  In order to gain more insight into the conformation of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate (1) experimentally, some appropriate reactions of 1 and its derivative (S,S)-3, which bears isopropylidene protecting groups, have been executed. The stereochemical outcomes of such reactions as the Diels-Alder reaction, osmium tetraoxide-catalyzed hydroxylation, conjugate addition with amines, and cyclopropanation with phosphonium ylides point to a rigid conformation (1A) in which the vicinal TBDMSO groups, the most bulky substituents, are arranged in an anti relationship, and, therefore, the enoate groups are forced to be gauche each other. A dichroic exciton chirality study has also provided clear-cut evidence for this rigid conformation.

  DOI：

  10.1021/jo00075a024

文献信息

• <i>e</i><i>xo</i>-Selective Asymmetric Diels−Alder Reaction Catalyzed by Diamine Salts as Organocatalysts
  作者：Taichi Kano、Youhei Tanaka、Keiji Maruoka

  DOI：10.1021/ol060621i

  日期：2006.6.1

  [reaction: see text] A novel binaphthyl-based diamine (R)-2 was designed and synthesized. A protonic acid-(R)-2 salt catalyst has the advantage of exhibiting unprecedented high exo selectivity in the asymmetric Diels-Alder reaction of alpha,beta-unsaturated aldehydes. For instance, the reaction between cinnamaldehyde and cyclopentadiene in the presence of 12 mol % of binaphthyl-based diamine (R)-2

  [反应：见正文]设计并合成了一种新型的基于联萘基的二胺（R）-2。质子酸-（R）-2盐催化剂的优点是在α，β-不饱和醛的不对称Diels-Alder反应中显示出前所未有的高外切选择性。例如，肉桂醛和环戊二烯之间的反应在-下，在12 mol％的联萘基二胺（R）-2和10 mol％的p-TsOH.H（2）O在α，α，α-三氟甲苯中存在- 20℃下得到相应的exo环加合物，其中ee为主要的非对映异构体，为92％（exo / endo ＝ 13/1）。
• Effect of the U-Shaped Cavity of Conformationally Flexible Chiral Lewis-Acidic Boron-Based Catalysts in Multiselective Diels–Alder Reactions
  作者：Tatsuhiro Sakamoto、Kohei Toh、Kai Matsui、Manabu Hatano、Kazuaki Ishihara

  DOI：10.1021/acs.orglett.4c01060

  日期：2024.5.3

  flexible chiral Lewis acidic boron-based catalysts in multiselective Diels–Alder reactions was investigated. The U-shaped catalysts can recognize substituents at the terminal acetylene moiety of propynal based on steric factors and can also recognize alkyne and alkene substrates based on the match/mismatch between the catalysts and substrates. Moreover, even in a mixture of different catalysts and substrates

  研究了构象灵活的手性路易斯酸性硼基催化剂的 U 形腔在多选择性狄尔斯-阿尔德反应中的影响。 U型催化剂可以基于空间因子识别丙醛末端乙炔部分的取代基，还可以基于催化剂和底物之间的匹配/不匹配来识别炔烃和烯烃底物。此外，即使在不同催化剂和底物的混合物中，所需的竞争反应也可以多选择性地进行。这项概念验证研究应有助于体外人工酶类催化的发展。