dimethyl (2aR,3S,8R,8aS)-2a,3,8,8a-tetrahydro-3,8-epoxycyclobuta[b]naphthalene-1,2-dicarboxylate | 71928-62-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: dimethyl (2aR,3S,8R,8aS)-2a,3,8,8a-tetrahydro-3,8-epoxycyclobuta[b]naphthalene-1,2-dicarboxylate
• CAS: 71928-62-6
• 化学式: C₁₆H₁₄O₅
• 分子量: 286.284
• InChiKey: NFFCBWCGZGWQJS-IOQCUFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  dimethyl (2aR,3S,8R,8aS)-2a,3,8,8a-tetrahydro-3,8-epoxycyclobuta[b]naphthalene-1,2-dicarboxylate 在 叔丁基过氧化氢 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 6.0h， 生成 dimethyl (1α,2β,3α,10α,11β,12α,13β,14α,21α,22β)-23,24,25-trioxaoctacyclo[10.10.1.1(3,10).1(14,21).0(2,11).0(4,9).0(13,22).0(15,20)]pentacosa-4,6,8,15,17,19-hexaene-1,12-dicarboxylate
  参考文献：
  名称：

  顺-Facial杂桥连[ Ñ ] polynorbornanes：一类新的polarofacial框架分子的稠合的7-氧杂-和7- azanorbornanes组成

  摘要：

  新氧桥降冰片烷-稠合环丁烯环氧化物和双- （环丁烯环氧化物）中描述和示出为7-azanorbornenes以产生立体选择性反应顺式-facial Ñ，ö -bridged polynorbornanes和stereorandomly 7-oxanorbornenes以产生ö，ö -桥接polynorbornanes作为混合物顺式-facial和抗-facial产品。1个含有多达六个Polarofacial系统SYN -facial降冰片烷桥描述的，当具有七个共面的氧原子系统已经制备通过将末端环氧环至O 5-[5]聚降冰片烷。酯取代的1,3,4-恶二唑被示出为是有用的试剂，用于耦合7- oxanorbornanes和主要产生顺-facial ö -bridged polarofacial与它们一起系统抗-facial异构体。

  DOI：

  10.1016/s0040-4020(00)01027-9
• 作为产物：
  描述：

  1,4-二氢-1,4-环氧萘 、 丁炔二酸二甲酯 在 RuH₂(CO)(PPh₃)₃ 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以38%的产率得到dimethyl (2aR,3S,8R,8aS)-2a,3,8,8a-tetrahydro-3,8-epoxycyclobuta[b]naphthalene-1,2-dicarboxylate
  参考文献：
  名称：

  微波加速钌催化的 [2π + 2π] 二甲基乙炔二羧酸酯与降冰片烯的环加成反应

  摘要：

  摘要 已经开发了一种高效便捷的方法，用于钌催化的二甲炔二甲酸与降冰片烯的 [2π + 2π] 环加成反应。在微波条件下反应显着加速，而常用的苯溶剂被环境友好的四氢呋喃取代。

  DOI：

  10.1080/00397911.2010.481744

文献信息

• In-Line Proximity Effects in Extended 7-Azanorbornanes. 1. A New Concept for Modifying Effector Group Separation Based on the Control of <i>N</i>-Invertomer Geometry
  作者：Douglas N. Butler、Malcom L. A. Hammond、Martin R. Johnston、Guangxing Sun、John R. Malpass、John Fawcett、Ronald N. Warrener

  DOI：10.1021/ol9910969

  日期：2000.3.1

  Control of N-substituent geometry in fused 7-azanorbornane systems is based on the dominance of one proximate bridge (sentinel X) over the other (sentinel Y) relative to the N-bridge; the N-inversion equilibrium can effectively be displaced in favor of a single invertomer. This study has used a combination of synthesis, crystallography, and molecular modeling to establish stereostructures.

  稠合7-氮杂硼硼烷系统中N取代基几何结构的控制基于一个相对于N桥的邻近桥（前哨X）相对于另一个桥（前哨Y）的优势。N转化平衡可以有效地取代单个转化聚合物。这项研究结合了合成，晶体学和分子模型来建立立体结构。
• A cascade thermal isomerisation of cyclobutane di-(carbomethoxy) Δ2-1,2,3-triazolines with intramolecular 1,3-dipolar cycloreversion as the key step
  作者：Davor Margetić、Ronald N. Warrener、Douglas N. Butler、Chuan-Ming Jin

  DOI：10.1016/j.tet.2012.02.073

  日期：2012.4

  quantum chemical calculations have been used to support a postulated reaction mechanism involving as the first step, a rare example of intramolecular 1,3-dipolar cycloreversion. Subsequently, several steps involving 1,3-dipolar ring closure, hydrogen shifts and an intramolecular addition are postulated leading to the observed product of this deep-seated isomerisation. The influence of changing substituents

  应变Δ的前所未有的热异构化2导致的产物的形成-1,2,3- triazolines具有一种新颖的1,2,7-三氮杂双环[3.3.0]辛-2-烯环在降冰片烷骨架引入系统。实验证据和量子化学计算已用于支持假设的反应机理，该反应机理涉及第一步，分子内1,3-偶极环还原的罕见例子。随后，提出了涉及1,3-偶极环闭合，氢转移和分子内加成的几个步骤，导致观察到这种深层异构化的产物。还研究了取代基的变化对这种新型反应级联产物结果的影响。
• Dipolar Cycloaddition Reactions of Azomethine Ylides Generated by endocyclic-exocyclic 1,3-dipole Rearrangement
  作者：Davor Margetić、Ronald N. Warrener、Douglas N. Butler、Craig M. Holland

  DOI：10.1002/jhet.2167

  日期：2015.9

  Dipolar cycloaddition of polycyclic azomethine ylides, in which the central nitrogen atom is part of a pyrrolidine ring and bears a methoxycarbonyl group with norbornenes has been shown to produce two main types of products featuring pyrrolizidine rings. In conjuction with results of quantum chemical calculations (B3LYP), mechanistic rationale was postulated. The key reaction step is unprecedented

  已显示多环偶氮甲亚胺的双极环加成反应产生两种主要类型的具有吡咯嗪环的产物，其中中心氮原子是吡咯烷环的一部分，并带有降冰片烯。结合量子化学计算（B3LYP）的结果，提出了机械原理。关键的反应步骤是通过分子间的质子迁移（形式[1,3] H位移）实现空前的环内至环外甲亚胺叶立德重排。
• ——
  作者：Douglas N. Butler、Brian Halton、John Warkentin、Ronald N. Warrener

  DOI：10.1071/ch00077

  日期：——

  Dimethoxycarbene, generated from 2,2- dimethoxy- 5,5- dimethyl-Delta (3)-1,3,4-oxadiazoline (8), adds to the electron-deficient double bond of ring-fused cyclobutene diesters (11), (12) and (15) from the face remote from the methano bridge to give the respective bicyclo[2.1.0] pentanone acetals (13), (14) and (16). In two cases, dimethylcyclopropanes (17) and (24) also formed as by-products in these reactions. Mechanisms for the formation of all products and by-products are proposed, especially in regard to an unusual 1,3-dipolar cycloaddition product (23) isolated from the reaction of (8) with (11). Hydrolysis of acetal (13) to the ring-fused cyclopropanone (27) is thwarted by preferential release of ring strain of an external cyclopropyl carbon-carbon bond. In acid media this results in the formation of a benzonorbornane-fused cyclobutane triester (26) with proton capture from the same face, likely from concerted methoxy group-assisted opening of the three-membered ring. Kinetic product (26) is isomerized to the thermodynamic isomer (30) with sodium methoxide. Attempted deacetalization of (13) with iodotrimethylsilane gives (26) when traces of acid are present, but provides the thermodynamic product (30) directly in the presence of pyridine.