2,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: 2,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde
• 英文别名: (1R,2S,3R,4S)-2,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: MWIMNADEOQZXBT-IMSYWVGJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde 在 sodium tetrahydroborate 作用下， 生成 ((1R,2S,3R,4S)-2,3-Dimethyl-bicyclo[2.2.1]hept-5-en-2-yl)-methanol
  参考文献：
  名称：

  Strained silacycle-catalyzed asymmetric Diels–Alder cycloadditions: the first highly enantioselective silicon Lewis acid catalyst

  摘要：

  The first highly enantioselective silicon Lewis acid catalyst for an asymmetric organic transformation has been developed. The catalyst derives its activity from the strain induced in the silicon center by virtue of being constrained in a five-membered ring. A simple tridentate ligand has been developed and the derived chlorosilane complex catalyzes the Diels-Alder cycloaddition of methacrolein and cyclopentadiene with 94% ee. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.076
• 作为产物：
  描述：

  反式-2-甲基-2-丁烯醛 、 环戊二烯 在 C₃₃H₃₂BF₃NO₅P*2C₁₈BF₁₅ 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以80%的产率得到2,3-dimethylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde
  参考文献：
  名称：

  基于CN···B和PO···B配位键的手性超分子路易斯酸催化剂对映选择性Diels-Alder反应

  摘要：

  以手性3-磷酰基-1,1'-双-2-萘酚、(2-氰基苯基)硼酸和三(五氟苯基)硼烷为原料，通过CN…B和PO·结合制备手性超分子硼路易斯酸催化剂··B协调键。特别是，配位的三（五氟苯基）硼烷以路易斯酸辅助路易斯酸催化剂体系的方式增加了活性中心的路易斯酸度。这些催化剂中可能存在的空腔非常适合丙烯醛与环状或非环状二烯的几种 Diels-Alder 探针反应，从而以良好到高产率和高对映选择性得到相应的加合物。

  DOI：

  10.1055/s-0035-1561362

文献信息

• Diazepane Carboxylates as Organocatalysts in the Diels-Alder Reaction of α-Substituted Enals
  作者：Nicklas O. Häggman、Benjamin Zank、HyunJune Jun、Dainis Kaldre、James L. Gleason

  DOI：10.1002/ejoc.201801009

  日期：2018.10.24

  Diazepane carboxylates efficiently catalyze the Diels–Alder cycloaddition of α‐substituted enals with a range of dienes. With chiral diazepane backbones, weak electrostatic interactions favour diene approach from the more hindered face, leading to enantioselectivities of 70–95 % with a range of dienophiles.

  地西羧酸盐可有效催化α-取代的烯类与一系列二烯的狄尔斯-阿尔德环加成反应。对于手性二氮杂庚烷骨架，较弱的表面会产生弱的静电相互作用，从而有利于二烯方法，导致一系列亲二烯体的对映选择性为70–95％。
• Remote Tris(pentafluorophenyl)borane-Assisted Chiral Phosphoric Acid Catalysts for the Enantioselective Diels–Alder Reaction
  作者：Kazuaki Ishihara、Manabu Hatano、Hideyuki Ishihara、Yuta Goto

  DOI：10.1055/s-0035-1560369

  日期：——

  supramolecular phosphoric acid catalysts were developed for the model Diels–Alder reaction of α-substituted acroleins with cyclopentadiene. Two remotely coordinated tris(pentafluorophenyl)boranes should help to increase the Bronsted acidity of the active center in the supramolecular catalyst and create effective bulkiness for the chiral cavity. The prepared supramolecular catalysts acted as not only conjugated

  三（五氟苯基）硼烷辅助的手性超分子磷酸催化剂被开发用于α-取代丙烯醛与环戊二烯的模型 Diels-Alder 反应。两个远程协调的三（五氟苯基）硼烷应该有助于增加超分子催化剂中活性中心的布朗斯台德酸度，并为手性空腔创造有效的体积。制备的超分子催化剂不仅可以作为共轭布朗斯台德酸-布朗斯台德碱催化剂，而且还可以作为双功能路易斯酸-布朗斯台德碱催化剂，添加中心非手性路易斯酸源如儿茶酚硼烷。
• Catalytic enantioselective construction of all-carbon quaternary stereocenters by an organocatalytic Diels–Alder reaction of α-substituted α,β-unsaturated aldehydes
  作者：Taichi Kano、Youhei Tanaka、Kenta Osawa、Taiga Yurino、Keiji Maruoka

  DOI：10.1039/b819034h

  日期：——

  A binaphthyl-based primary amine (R)- was designed for the Diels-Alder reaction of alpha-substituted alpha,beta-unsaturated aldehydes; in the presence of the TfOH salt of (R)-, the Diels-Alder reaction of alpha-substituted alpha,beta-unsaturated aldehydes with cyclopentadiene proceeded to afford the corresponding cycloadducts having one all-carbon quaternary stereocenter in good yield with good to

  设计了一种基于二萘基的伯胺（R），用于α-取代的α，β-不饱和醛的Diels-Alder反应；在（R）-的TfOH盐的存在下，α-取代的α，β-不饱和醛与环戊二烯的狄尔斯-阿尔德反应进行，从而以高收率和高收率提供了具有一个全碳四元立体中心的相应的环加合物。立体选择性。
• A Novel Chiral Super-Lewis Acidic Catalyst for Enantioselective Synthesis
  作者：Yujiro Hayashi、Jeffrey J. Rohde、E. J. Corey

  DOI：10.1021/ja960766s

  日期：1996.1.1
• Strained silacycle-catalyzed asymmetric Diels–Alder cycloadditions: the first highly enantioselective silicon Lewis acid catalyst
  作者：Katsumi Kubota、Christopher L. Hamblett、Xiaolun Wang、James L. Leighton

  DOI：10.1016/j.tet.2006.06.076

  日期：2006.12

  The first highly enantioselective silicon Lewis acid catalyst for an asymmetric organic transformation has been developed. The catalyst derives its activity from the strain induced in the silicon center by virtue of being constrained in a five-membered ring. A simple tridentate ligand has been developed and the derived chlorosilane complex catalyzes the Diels-Alder cycloaddition of methacrolein and cyclopentadiene with 94% ee. (c) 2006 Elsevier Ltd. All rights reserved.