(S)-(-)-methyl 1-oxo-2-(3'-oxobutyl)-2-indanecarboxylate | 58623-84-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: (S)-(-)-methyl 1-oxo-2-(3'-oxobutyl)-2-indanecarboxylate
• 英文别名: methyl (2S)-3-oxo-2-(3-oxobutyl)-1H-indene-2-carboxylate
• CAS: 58623-84-0
• 化学式: C₁₅H₁₆O₄
• 分子量: 260.29
• InChiKey: WNCJANBKGLLOHU-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-(-)-methyl 1-oxo-2-(3'-oxobutyl)-2-indanecarboxylate 在 四氢吡咯 、 4-甲基苯磺酸吡啶 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 116.0h， 生成 (S)-3,3-ethylenedioxy-9a-methoxycarbonyl-1,2,9,9a-tetrahydro-3H-fluorene
  参考文献：
  名称：

  Synthesis of (R)-(-)-3-Methoxymethyl-3-propyl-3,4-dihydrocoumarin from a Chiral Michael Adduct: Absolute Configurations of the Allylated Products of Enantioselective Radical-Mediated Reactions.

  摘要：

  (R)-3-甲氧基甲基-3-丙基-3,4-二氢香豆素是从手性迈克尔加成物（(S)-甲基2,3-二氢-1-氧代-2-(3-氧代丁基)-1H-茚-2-羧酸酯）合成的，目的是确定通过手性自由基介导的烯丙基化反应得到的产品的绝对构型。迈克尔加成物的醛缩环反应在抑制逆迈克尔反应的情况下顺利进行，从而得到具有光学活性的环化产物。在BF3·Et2O存在下，(R)-2-甲氧基甲基-2-丙基茚满酮的Baeyer-Villiger反应得到所需二氢香豆素。

  DOI：

  10.1248/cpb.47.1380
• 作为产物：
  描述：

  1-Oxo-1H-indene-2-carboxylic acid methyl ester 、 丁烯酮 生成 (S)-(-)-methyl 1-oxo-2-(3'-oxobutyl)-2-indanecarboxylate
  参考文献：
  名称：

  DESIMONI, G.;QUADRELLI, P.;RIGHETTI, P. P., TETRAHEDRON, 46,(1990) N, C. 2927-2934

  摘要：

  DOI：

文献信息

• Enantioselective Michael reaction of β-keto esters organocatalyzed by recoverable Cinchona-derived dimeric ammonium salts
  作者：Silvia Tarí、Rafael Chinchilla、Carmen Nájera

  DOI：10.1016/j.tetasy.2009.11.007

  日期：2009.12

  Dimeric anthracenyldimethyl-derived Cinchona ammonium salts are used as chiral organocatalysts in 1–10 mol % for the enantioselective conjugate addition of 2-alkoxycarbonyl-1-indanones to β-unsubstituted Michael acceptors. The corresponding adducts bearing a new all-carbon quaternary center were usually obtained in high yield and with up to 94% ee when using ammonium salts derived from quinidine and

  二聚蒽烯基二甲基衍生的金鸡纳铵盐以1-10 mol％的比例用作手性有机催化剂，用于将2-烷氧基羰基-1-茚满酮对映体选择性共轭加成至β-未取代的Michael受体上。当使用衍生自奎尼丁及其假对映体奎宁的铵盐作为有机催化剂时，通常可以高收率获得最高94％ee的带有新的全碳季中心的相应加合物。这些催化剂几乎可以通过在乙醚中沉淀而定量回收并再利用。
• Recoverable Cinchona ammonium salts as organocatalysts in the enantioselective Michael addition of β-keto esters
  作者：Silvia Tarí、Rafael Chinchilla、Carmen Nájera

  DOI：10.1016/j.tetasy.2010.11.016

  日期：2010.12

  Several dimeric Cinchona-alkaloid anthracenyldimethyl-derived ammonium salts, are used as organocatalysts in the enantioselective Michael addition reaction of cyclic β-keto esters to α,β-unsaturated carbonyl compounds, in the presence of diisopropylethylamine as a base (30 mol %), for the generation of enantiomerically enriched adducts bearing quaternary stereocenters. Quinine and quinidine-derived

  在二异丙基乙胺为碱（30摩尔％）的情况下，几种二聚Cinchona-生物碱蒽基二甲基蒽盐被用作环状β-酮酯与α，β-不饱和羰基化合物的对映选择性Michael加成反应中的有机催化剂。用于生成带有四级立体中心的对映体富集的加合物。奎宁和奎尼丁衍生的二聚铵盐（1-10 mol％）以较高的收率（最高98％）提供了相应的加合物（最高94％ee）的相反和更高的对映选择性。取代的2-烷氧基羰基-1-茚满酮用作亲核试剂的前体，以及2-氧代环戊烷甲酸乙酯和叔酸乙酯2,5-二氧杂-1-苯基吡咯烷-3-羧酸丁酯。这些有机催化剂可在反应结束时通过在乙醚中沉淀而回收，并在不损失任何活性的情况下重复使用。
• Enantioselective Robinson-Type Annulation Reaction Catalyzed by Chiral Phosphoric Acids
  作者：Takahiko Akiyama、Takuya Katoh、Keiji Mori

  DOI：10.1002/anie.200901127

  日期：2009.5.25

  differences: Implementation of an enantioselective Michael addition followed by an intramolecular aldol reaction catalyzed by two phosphoric acids has enabled the synthesis of cyclohexenone derivatives with excellent enantioselectivities. Prominent kinetic resolution was observed in the latter reaction. Ar=aromatic group, X=H, halogen, Y=H, Me, halogen.

  让我们解决分歧：实现对映选择性迈克尔加成反应，然后通过两种磷酸催化的分子内羟醛反应，可以合成具有优异对映选择性的环己烯酮衍生物。在后一反应中观察到明显的动力学拆分。Ar ＝芳族基团，X ＝ H，卤素，Y ＝ H，Me，卤素。
• Creation of monomeric La complexes on apatite surfaces and their application as heterogeneous catalysts for Michael reactions
  作者：Kohsuke Mori、Michitaka Oshiba、Takayoshi Hara、Tomoo Mizugaki、Kohki Ebitani、Kiyotomi Kaneda

  DOI：10.1039/b512030f

  日期：——

  Using a cation-exchange method, an equimolar substitution of La3+ for Ca2+ occurred by the treatment of stoichiometric hydroxyapatite (HAP: Ca10(PO4)6(OH)2) with an aqueous solution of La(OTf)3, affording a monomeric hydroxyapatite-bound La complex (LaHAP). Physicochemical characterization by means of XRD, XPS, IR, and La K-edge XAFS analyses proved that a monomeric La3+ phosphate complex was generated on its surface. Such monomeric La3+ species function as an efficient heterogeneous catalyst for the Michael reaction of 1,3-dicarbonyls with enones under aqueous or solvent-free conditions. The work-up procedure is straightforward and the spent catalyst could be recycled without any loss of the catalytic activity. Further application to an asymmetric version was also investigated using various apatite catalysts modified with chiral organic ligands. Enantioselectivity was found to depend on the chiral ligand, solvent, and rare earth metal triflate precursor (RE(OTf)3) for the reaction of methyl 1-oxoindan-2-carboxylate with methyl vinyl ketone. Under optimized reaction conditions, a monomeric fluoroapatite-bound La complex catalyst modified with (R,R)-tartaric acid (TA-LaFAP) provided the Michael adduct quantitatively in up to 60% ee.

  采用阳离子交换法，通过将化学计量的羟基磷灰石（HAP：Ca\(}_10}\)(PO\(}_4}\))\(}_6}\)(OH)\(}_2}\)）与La(OTf)\(}_3}\)的水溶液处理，实现了La\(}^3+}\)对Ca\(}^2+}\)的等摩尔取代，得到了单体羟基磷灰石结合的镧配合物（LaHAP）。通过XRD、XPS、IR和La K边XAFS分析的物理化学表征证明，在其表面生成了单体La\(}^3+}\)磷酸盐配合物。这种单体La\(}^3+}\)物种作为高效的非均相催化剂，在水相或无溶剂条件下对1,3-二羰基化合物与烯酮的迈克尔加成反应具有催化作用。后处理过程简单，且催化剂可回收，无催化活性损失。此外，还研究了通过各种含手性有机配体的磷灰石催化剂的进一步应用，以实现不对称版本。在甲基1-氧茚-2-羧酸酯与甲基乙烯基酮的反应中，产物的对映选择性取决于手性配体、溶剂和稀土金属三氟甲磺酸盐前体（RE(OTf)\(}_3}\)）。在优化的反应条件下，经过(R,R)-酒石酸（TA-LaFAP）修饰的单体氟磷灰石结合的镧配合物催化剂，能使迈克尔加成产物达到定量收率，最高对映体过量值达60%。
• Copper(II) in organic synthesis. VIII enantioselective michael reactions with chiral copper(II) complexes as catalysts
  作者：G. Desimoni、P. Quadrelli、P.P. Righetti

  DOI：10.1016/s0040-4020(01)88385-x

  日期：1990.1

  - Using copper(II) chiral complexes as catalysts, enantioselective Michael reactions were performed. The degree of enantioselectivity depended on the design of the catalyst and the best results (70% e.e.) were obtained with tetradentate ligands.

  -使用铜（II）手性配合物作为催化剂，进行对映选择性迈克尔反应。对映选择性的程度取决于催化剂的设计，四齿配体可获得最佳结果（70％ee）。