(-)-benzyl-(1S,2S,3R,4R)-3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate | 90819-99-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (-)-benzyl-(1S,2S,3R,4R)-3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate
• 英文别名: benzyl (1S,2S,3R,4R)-3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 90819-99-1
• 化学式: C₁₆H₁₈O₂
• 分子量: 242.318
• InChiKey: DZZPIKFDBDFCEP-BEAPCOKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  在 CPBA 作用下， 生成 (-)-benzyl-(1S,2S,3R,4R)-3-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  Recoverable Chiral Sulfoxide: Asymmetric Diels–Alder Reaction Using Optically Active 1-(2-p-Tolylsulfinyl)pyrrolylα,β-Unsaturated Ketones as a Dienophile

  摘要：

  手性肉桂酰基和克罗托尼基（2-p-甲苯磺酰基）吡咯与环戊二烯在AlCl3或Yb(OTf)3的存在下进行Diels–Alder反应，顺利生成相应的内近亲加成产物，产率极高，非对映选择性范围在92%至99% d.e. 经过加成产物的醇解，手性辅助剂2-吡咯磺氧化物被高效回收，且未损失光学纯度。

  DOI：

  10.1246/cl.1997.145

文献信息

• (5R)-7,8:9,10-Di-O-isopropylidene-2,6-dioxa-4-azaspiro[4,5]decan-3-one: a new chiral spirooxazolidin-2-one derived from D-(+)-galactose for use in asymmetric transformations
  作者：Malcolm R. Banks、Alexander J. Blake、J. I. G. Cadogan、Ian M. Dawson、Suneel Gaur、Ian Gosney、Robert O. Gould、Keith J. Grant、Philip K. G. Hodgson

  DOI：10.1039/c39930001146

  日期：——

  Starting from D-(+)-galactose, the crystalline spirooxazolidin-2-one 2 can be readily prepared in an optically pure state by a nitrene-mediated four-step sequence, and serves to control both aldol and Diels–Alder reactions with high chiral efficiency, being easy to remove after use.

  从D-(+)-半乳糖出发，通过亚氮中间体介导的四步反应序列，可以方便地制备手性纯的结晶螺恶唑啉酮2，它在使用后易于去除，并且能够高效地控制醛醇反应和狄尔斯-阿尔德反应。
• Asymmetric Diels−Alder, Michael, and Aldol Reactions Using a Planar Chiral 1,3-Oxazol-2(3<i>H</i>)-one Derived from (<i>R</i>)-(+)-4-Hydroxy-[2.2]paracyclophane
  作者：Antonio Cipiciani、Francesco Fringuelli、Oriana Piermatti、Ferdinando Pizzo、Renzo Ruzziconi

  DOI：10.1021/jo016383g

  日期：2002.4.1

  (+)-(R)-[2.2]Paracyclophane[4,5-d]-1,3-oxazol-2(3H)-one exhibiting planar chirality has been used as a chiral auxiliary in asymmetric Diels-Alder, Michael, and aldol reactions of alpha,beta-unsaturated carboxy and enolate imides, respectively. The endo-exo- and face-diastereoselectivity is good and is controlled by the spatial relationship between the prochiral center and the C9-C10 ethylene bridge

  （+）-（R）-[2.2]吡喃环[4,5-d] -1,3-恶唑-2（3H）-具有平面手性的化合物已被用作不对称Diels-Alder的手性助剂，Michael，和α，β-不饱和羧基和烯醇酰亚胺的醛醇缩合反应。内-外-对-非-对映体选择性良好，并由前手性中心与[2.2]对环环烷部分的C9-C10亚乙基桥之间的空间关系控制。手性助剂易于除去并定量回收。
• Stereocontrolled diels-alder reactions with chiral tricyclic oxazolidinones
  作者：Kazuhiko Tanaka、Hiroe Uno、Hideji Osuga、Hitomi Suzuki

  DOI：10.1016/s0957-4166(00)80165-2

  日期：1993.4

  (1R,2R,6S,7S)-5-Aza-1,10,10-trimethyl-3-oxatricyclo[5.2.1.02,6]decan-4-one (endo-oxazolidinone) and (1R,2S,6R,7S)-isomer (exo-oxazolidinone) are found to be efficient diastereomeric auxiliaries for Diels-Alder reactions, which are promoted by Lewis acid catalysts with predictable absolute stereochemistry. Thus, the reaction of cyclopentadiene with N-crotonyl- or N-cinnamoyl-endo-oxazolidinones gave (1R,2R,3S,4S)-3-methyl- or (1R,2S,3S,4S)-3-phenylbicyclo[2.2.1]hept-5-ene-2-carboxylates, while their enantiomers, i.e. (1S,2S,3R,4R)-3-methyl- or (1S,2R,3R,4R)-3-phenylbicyclo[2.2.1]hept-5-ene-2-carboxylates were obtained stereoselectively from the corresponding exo-oxazolidinone derivatives.

  (1R,2R,6S,7S)-5-氮杂-1,10,10-三甲基-3-氧杂三环[5.2.1.02,6]十碳-4-酮（内-氧杂环丁酮）及其(1R,2S,6R,7S)-异构体（外-氧杂环丁酮）被发现是高效的非对映异构Diels-Alder反应辅助剂，这些反应由路易斯酸催化剂促进，并具有可预测的绝对构型。因此，环戊二烯与N-肉桂酰基或N-肉桂酰基-内-氧杂环丁酮的反应生成了(1R,2R,3S,4S)-3-甲基或(1R,2S,3S,4S)-3-苯基双环[2.2.1]庚-5-烯-2-羧酸酯，而它们的对映体，即(1S,2S,3R,4R)-3-甲基或(1S,2R,3R,4R)-3-苯基双环[2.2.1]庚-5-烯-2-羧酸酯，则通过相应的外-氧杂环丁酮衍生物以高立体选择性获得。
• Asymmetric Diels-Alder Reaction of 2-(p-Tolylsulfinyl)-1-indolyl a,b-Unsaturated Enones
  作者：Yoshitsugu Arai、Takeshi Katori、Yukio Masaki

  DOI：10.3987/com-06-10695

  日期：——

  The asymmetric Diels-Alder reaction of chiral l-[2-(p-tolylsulfinyl)-indolyl enones was examined. The cycloaddition of cinnamyl and crotonyl α,β-unsaturated enones with cyclopentadiene in the presence of a lanthanoid triflate as a Lewis acid proceeds smoothly to give the corresponding endo cycloadducts with high diastereoselectivity.

  检测了手性 l-[2-(p-tolylsulfinyl)-indolyl enones 的不对称 Diels-Alder 反应。在作为路易斯酸的镧系元素三氟甲磺酸盐存在下，肉桂基和巴豆基α,β-不饱和烯酮与环戊二烯的环加成反应顺利进行，得到具有高非对映选择性的相应内环加成物。
• Asymmetric Diels-Alder cycloaddition reactions with chiral .alpha.,.beta.-unsaturated N-acyloxazolidinones
  作者：David A. Evans、K. T. Chapman、J. Bisaha

  DOI：10.1021/ja00212a037

  日期：1988.2