diisopropyl cis-2,3-Dihydro-1H-indene-3a,7a-dicarboxylate | 881839-06-1

• 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: diisopropyl cis-2,3-Dihydro-1H-indene-3a,7a-dicarboxylate
• 英文别名: dipropan-2-yl (3aS,7aR)-2,3-dihydro-1H-indene-3a,7a-dicarboxylate
• CAS: 881839-06-1
• 化学式: C₁₇H₂₄O₄
• 分子量: 292.375
• InChiKey: SSSTXLPRDQFFRN-CALCHBBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diisopropyl cis-2,3-Dihydro-1H-indene-3a,7a-dicarboxylate 在 萘 、 lithium 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 0.52h， 以85%的产率得到diisopropyl trans-(6Z,8Z)-cyclonona-6,8-diene-1,5-dicarboxylate
  参考文献：
  名称：

  A Two-Step, Stereoselective Synthesis of Nine- and Ten-Membered Carbocycles from Phthalates

  摘要：

  A two-step, stereoselective procedure for the synthesis of nine- and ten-membered carbocycles from readily available phthalates is described. A variety of dialkyl phthalates have been transformed into [6,n]-fused bicyclo systems (n = 5, 6, 7) by a dearomatization/cyclization process and then converted into cyclonona- and cyclodecadienes through a bond cleavage reaction, whereby both processes are promoted by alkaline metals in THF.

  DOI：

  10.1021/acs.orglett.5b00552
• 作为产物：
  描述：

  1,3-二碘丙烷 、 邻苯二甲酸二异丙酯 在 (trimethylstannyl)lithium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 以99%的产率得到diisopropyl cis-2,3-Dihydro-1H-indene-3a,7a-dicarboxylate
  参考文献：
  名称：

  Me3SnLi通过stanna-Brook重排促进了芳族和杂芳族二酯的脱芳香化-双烷基化。

  摘要：

  Me3SnLi与芳族和杂芳族二酯的反应通过快速的stanna-Brook重排进行，该重排生成稳定的双烯酸酯，该双烯酸酯可在一个区域内进行区域选择性烷基化和环化，生成含6,5-，6,6-和6-环戊二烯的双环化合物6,7稠环系统。

  DOI：

  10.1021/ol053130r

文献信息

• C–C Bond-Forming and Bond-Breaking Processes from the Reaction of Diesters with Me₃SnLi. Synthesis of Complex Bridged Polycycles and Dialkyl Aromatic Compounds
  作者：Lucas Martínez-García、Rubén Lobato、Gustavo Prado、Pablo Monje、F. Javier Sardina、M. Rita Paleo

  DOI：10.1021/acs.joc.8b02891

  日期：2019.2.15

  followed by a reaction of the resulting unsaturated diesters with Me3SnLi. We propose that a stanna-Brook rearrangement plays a fundamental role in the formation of the polycyclic organotin acetals obtained. These unusual compounds could be further functionalized by tin–lithium exchange followed by alkylation of the newly formed tertiary carbanion. Alternatively, dialkylated aromatic hydrocarbons have

  1,2-芳族二酯可以通过两步程序转变为应变桥联多环结构，该程序包括由碱金属促进的初始还原烷基化，然后使所得的不饱和二酯与Me 3 SnLi反应。我们提出，斯坦纳-布鲁克重排在获得的多环有机锡缩醛的形成中起基本作用。这些不寻常的化合物可以通过锡-锂交换，然后对新形成的叔碳负离子进行烷基化来进一步功能化。或者，已经通过Me 3 SnLi促进的脱碳反应制备了二烷基化的芳族烃。1,4-芳族二酯经过还原二烷基化，然后通过与Me 3反应转化为降冰片二烯酮衍生物SnLi。从蒽38开始，仅用两步就制备了几种稳定的二苯并降冰片二烯酮41。相应的萘类似物得到1,4-二烷基萘。所描述的合成协议提供对通过现有合成方法不容易获得的结构的访问。
• Enantioselective Annulation Reactions of Bisenolates Prepared Through Dearomatization Reactions of Aromatic and Heteroaromatic Diesters
  作者：Jaime Pérez-Vázquez、Alberte X. Veiga、Gustavo Prado、F. Javier Sardina、M. Rita Paleo

  DOI：10.1002/ejoc.201101427

  日期：2012.2

  A one-pot, enantioselective strategy for the dearomatization–annulation of aromatic diesters to give a range of highly functionalized polycyclic molecules with excellent enantioselectivity is presented. This methodology is based on the reaction of bisenolates, prepared by treating aromatic diesters with trialkyltin lithium reagents, which involves a stanna-Brook rearrangement, with 1,ω-dihaloalkanes

  提出了一种用于芳族二酯脱芳构化-环化的单锅对映选择性策略，以提供一系列具有优异对映选择性的高度官能化多环分子。该方法基于双烯醇盐的反应，通过用三烷基锡锂试剂处理芳族二酯制备，该反应涉及 stanna-Brook 重排，与 1,ω-二卤代烷烃和其他双亲电子试剂。我们还开发了实验条件，通过将 Me6Sn2 原位回收到含有过量锂金属的 Me3SnLi 中，用亚化学计量的所需锡试剂进行这些反应，并提供了对这种合成方法的范围和局限性的研究。
• <i>Bis</i>-enolates with Extended π-Conjugation Are Powerful Nucleophiles: A Study of Their Alkylation Reactions with Very Hindered C-Electrophiles
  作者：Mariña Castroagudín、Rubén Lobato、Lucas Martínez-García、F. Javier Sardina、M. Rita Paleo

  DOI：10.1021/acs.joc.9b01961

  日期：2019.12.20

  Bis-enolates with extended π-conjugation, prepared by alkali metal-mediated reduction of several aromatic and unsaturated diesters, can be efficiently and regioselectively alkylated with very hindered C-electrophiles, such as neopentyl, secondary and tertiary alkyl halides, and tosylates. A one-step synthesis of 4-alkyl phthalates was derived from the reductive alkylation of a phthalate diester with hindered

  通过碱金属介导的几种芳族和不饱和二酯还原反应制备的具有扩展π共轭的双烯醇化物可以通过非常受阻的C-亲电试剂（例如新戊基，仲和叔烷基卤化物）和甲苯磺酸盐高效地进行区域选择性烷基化。邻苯二甲酸4-烷基酯的一步合成是通过邻苯二甲酸二酯与受阻卤化物的还原烷基化反应，然后再用氧气进行重新麦芽糖化而完成的。另外，已经开发了合成方案以仅一步或两步就可以有效地从邻苯二甲酸二异丙酯制备复杂的稠合或螺二环自行车。
• Stereoselective Synthesis of Hydrindane and Hydroazulene Derivatives by Transannular Cyclization of Nine- and Ten-Membered Carbocycles
  作者：Lucas Martínez-García、Gustavo Prado、Karen V. Góñez、M. Rita Paleo、F. Javier Sardina

  DOI：10.1021/acs.joc.1c01751

  日期：2021.10.1

  transannular cyclization process that stereoselectively yields hydroazulenes and hydrindanes derivatives. Cyclononadienyl diesters, which can be isolated after the ring-opening step by judicious choice of the reaction conditions, undergo a tandem conjugate addition/intramolecular Michael addition upon treatment with chiral lithium amides to give bicyclic β-amino esters in a process where 4 contiguous stereocenters

  用锂/萘处理顺式稠合双环二烯二羧酸酯引发串联开环和跨环环化过程，立体选择性地产生氢化茚和氢化茚衍生物。环壬二烯基二酯可在开环步骤后通过明智地选择反应条件进行分离，在用手性氨基化锂处理后进行串联共轭加成/分子内迈克尔加成，在 4 个连续立体中心的过程中得到双环 β-氨基酯形成高非对映控制。作为这种方法的应用，已经开发了一种通往乌头碱型生物碱的高度对映体富集的 AEF 环核心的简明路线。起始顺式-融合的双环二羧酸容易在一个步骤中由二异丙基邻苯二甲酸酯的还原性烷基化制备（钠/ THF，随后适当的双-electrophiles）。
• A Two-Step, Stereoselective Synthesis of Nine- and Ten-Membered Carbocycles from Phthalates
  作者：Gustavo Prado、Alberte X. Veiga、Fernando Fernández-Nieto、M. Rita Paleo、F. Javier Sardina

  DOI：10.1021/acs.orglett.5b00552

  日期：2015.5.1

  A two-step, stereoselective procedure for the synthesis of nine- and ten-membered carbocycles from readily available phthalates is described. A variety of dialkyl phthalates have been transformed into [6,n]-fused bicyclo systems (n = 5, 6, 7) by a dearomatization/cyclization process and then converted into cyclonona- and cyclodecadienes through a bond cleavage reaction, whereby both processes are promoted by alkaline metals in THF.