dimethyl rac-(1S,2R,6S,7R)-5-oxotricyclo[5.2.1.02,6]dec-3-ene-3,4-dicarboxylate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: dimethyl rac-(1S,2R,6S,7R)-5-oxotricyclo[5.2.1.02,6]dec-3-ene-3,4-dicarboxylate
• 英文别名: exo-2,3-Bismethoxycarbonyl-4,7-methano-3a,4,5,6,7,7a-hexahydro-inden-1-on
• 化学式: C₁₄H₁₆O₅
• 分子量: 264.278
• InChiKey: NBEQEUBBWAONCL-RYPBNFRJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  69.67
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  降冰片烯 、 alkaline earth salt of/the/ methylsulfuric acid 在 十二/十四烷基二甲基氧化胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以74%的产率得到dimethyl rac-(1S,2R,6S,7R)-5-oxotricyclo[5.2.1.02,6]dec-3-ene-3,4-dicarboxylate
  参考文献：
  名称：

  On the behaviour of dimethyl acetylenedicarboxylate in carbonylation and Khand reactions

  摘要：

  Dimethyl acetylenedicarboxylate (DMAD) has been used as the alkyne component in the Khand reaction with norbornene under both thermal and N-oxide promoted conditions. Its thermolysis under CO pressure has also been reinvestigated and the structure of one of the trinuclear rearrangement products, MeO2C . CH2CCo3(CO)(9), confirmed by X-ray crystallography; (MeOOC)(2)CHCH(COOMe)(2) is the principal metal-free product from this reaction. Methyl but-2-ynoate undergoes similar rearrangement yielding MeO2C . CHMe . CCo3(CO)(9). (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)01202-9

文献信息

• Nitrous Oxide Promoted Pauson–Khand Cycloadditions
  作者：J. David Ricker、Vahid Mohammadrezaei、Thomas J. Crippen、Austin M. Zell、Laina M. Geary

  DOI：10.1021/acs.organomet.8b00810

  日期：2018.12.24

  The chemistry is done using equimolar amounts of alkyne, alkene, and dicobalt octacarbonyl, and is performed directly from the acetylenic component without having to presynthesize a cobalt-alkyne complex. Terminal acetylenes were suitable substrates, as was solid calcium carbide, and the corresponding adducts were isolated in good yields. Furthermore, two sequential [4+3] and [2+2+1] cycloadditions were

  描述了由羰基钴和一氧化二氮促进的炔烃，烯烃和一氧化碳的Pauson-Khand环加成反应以提供环戊烯酮。初步的机械实验表明，一氧化二氮的功能类似于在Pauson-Khand反应中通常使用的N-氧化物促进剂。由于活化机理，仅产生二氮和二氧化碳，因此避免了高分子量试剂和碱性副产物的积累。化学反应是使用等摩尔量的炔烃，烯烃和二钴八羰基化合物完成的，并且直接从炔属组分中进行，而无需预先合成钴-炔烃配合物。末端乙炔是合适的底物，固体电石也是合适的底物，并且以高收率分离出相应的加合物。此外，
• Co₂(CO)₈Catalyzed Pauson-Khand Reaction under Microwave Irradiation
  作者：Ulrich Groth、Stefan Fischer、Marc Jung、Andreas Schneider

  DOI：10.1055/s-2002-35561

  日期：——

  Microwave irradiation is used to accelerate Pauson-Khand reactions. The conditions for the Pauson-Khand reaction, catalytic in Co2(CO)8 under microwave irradiation, were optimized. It is possible to obtain various types of [2+2+1] cycloaddition products in 5 minutes without additional carbon monoxide.

  微波辐照用于加速保森-汉德反应。对微波辐照下在 Co2(CO)8 中催化 Pauson-Khand 反应的条件进行了优化。在不增加一氧化碳的情况下，可以在 5 分钟内得到各种类型的 [2+2+1] 环加成产物。
• Iron Carbonyl Induced Reactions of Norbornene Derivatives with Substituted Acetylenes
  作者：Kenji Hayakawa、Hans Schmid

  DOI：10.1002/hlca.19770600708

  日期：1977.11.2

  Photochemical reactions of norbornadiene with substituted acetylenes in the presence of Fe(CO)5 gave various products of different types, depending on the nature of the acetylene. The results are summarized in Table 1. The cyclopentanone 1 was always formed in these reactions. In the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, the cyclopentenones

  降冰片二烯与取代的乙炔在Fe（CO）5存在下的光化学反应，根据乙炔的性质，可得到各种不同类型的产物。结果总结在表1中。在这些反应中总是形成环戊酮1。在二取代的乙炔如乙炔二甲酸二甲酯和苯丙丙酸乙酯的反应中，分别形成了环戊烯酮2和5。相反，丙酸酯产生环己酮3和4，其中酯基相对于酮基连接在β碳上。方案7和8显示了形成这些产物的合理机制。二苯基乙炔的反应产生了环己烯二酮7以及环戊烯酮6。从苯乙炔的反应中获得了两个二烯产物8和9。通过在吡啶中与乙酸酐一起加热，将化合物9转化为芳族二乙酸酯13。在Fe（CO）5存在下进行辐照时，降冰片烯与乙炔二羧酸二甲酯和苯乙炔类似地反应，生成环戊烯酮14和环己烯酮15分别。加热后，化合物15异构化为对苯二酚16，其经乙酰化得到二乙酸酯17。
• On the behaviour of dimethyl acetylenedicarboxylate in carbonylation and Khand reactions
  作者：R.John Baxter、Graham R. Knox、Peter L. Pauson、Mark D. Spicer

  DOI：10.1016/s0022-328x(98)01202-9

  日期：1999.5

  Dimethyl acetylenedicarboxylate (DMAD) has been used as the alkyne component in the Khand reaction with norbornene under both thermal and N-oxide promoted conditions. Its thermolysis under CO pressure has also been reinvestigated and the structure of one of the trinuclear rearrangement products, MeO2C . CH2CCo3(CO)(9), confirmed by X-ray crystallography; (MeOOC)(2)CHCH(COOMe)(2) is the principal metal-free product from this reaction. Methyl but-2-ynoate undergoes similar rearrangement yielding MeO2C . CHMe . CCo3(CO)(9). (C) 1999 Elsevier Science S.A. All rights reserved.