(1R,3S,3aS,6aR)-4,6-dioxo-3,5-diphenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylic acid methyl ester

• 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: (1R,3S,3aS,6aR)-4,6-dioxo-3,5-diphenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylic acid methyl ester
• 英文别名: (1R,3S,3aS,6aR)-methyl 4,6-dioxo-3,5-diphenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate；(1S,3R,3aR,6aS)-methyl 4,6-dioxo-3,5-diphenyl-octahydropyrrol[3,4-c]pyrrol-1-carboxylate；methyl (1R,2R,4S,5S)-6,8-dioxo-4,7-diphenyl-3,7-diazabicyclo[3.3.0]octane-2-carboxylate；methyl 6,8-dioxo-4,7-diphenyl-3,7-diazabicyclo[3.3.0]octane-2-carboxylate；methyl (1S,3R,3aR,6aS)-4,6-dioxo-1,5-diphenyl-2,3,3a,6a-tetrahydro-1H-pyrrolo[3,4-c]pyrrole-3-carboxylate
• 化学式: C₂₀H₁₈N₂O₄
• 分子量: 350.374
• InChiKey: AXBMLULSXAJLDN-YLFCFFPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  75.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  N-苯基马来酰亚胺 、 Methyl (E)-N-benzylideneglycinate 在 (S)-(+)-5,5'-双[二(3,5-二叔丁基-4-甲氧基苯基)膦]-4,4'-二-1,3-苯并二氧戊环 、 copper(II) bis(trifluoromethanesulfonate) 、 三乙胺 作用下， 以 甲苯 为溶剂， 以64%的产率得到(1R,3S,3aS,6aR)-4,6-dioxo-3,5-diphenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Switching the Stereoselectivity: (Fullero)Pyrrolidines “a la Carte”

  摘要：

  Stereodivergent syntheses of cis/trans pyrrolidino[3,4:1,2]fullerenes and endo/exo pyrrolidines are reported with high enantioselectivity levels. Fullerenes are revealed as a useful benchmark to develop suitable catalysts to control the stereochemical outcome and to shed light on the mechanism involved in the related 1,3-dipolar cycloaddition.

  DOI：

  10.1021/ja306105b

文献信息

• Highly Enantioselective Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylide Catalyzed by a Copper(I)/ClickFerrophos Complex
  作者：Shin-ichi Fukuzawa、Hiroshi Oki

  DOI：10.1021/ol8003996

  日期：2008.5.1

  A copper(I)/ClickFerrophos complex catalyzed the asymmetric 1,3-dipolar cycloaddition reaction of methyl N-benzylideneglycinate (the source of azomethine ylides) with vinyl sulfone to give the exo-2,4,5-trisubstituted pyrrolidine in good yield with high enantioselectivity (99% ee). The complex also effectively catalyzed reactions of other dipolarophiles such as acrylates, maleate, and maleimides to

  铜（I）/ ClickFerrophos络合物催化N-亚苄基甘氨酸甲酯（偶氮甲亚胺基化物的来源）与乙烯基砜的不对称1,3-偶极环加成反应，以高收率得到exo-2,4,5-三取代的吡咯烷，高对映选择性（99％ee）。该配合物还有效地催化其他双亲性试剂如丙烯酸酯，马来酸酯和马来酰亚胺的反应，得到具有高非对映和对映选择性的exo-2,4,5-和2,3,4,5-取代的吡咯烷衍生物。
• A Cu^II-N,P Oxazolinylferrocene Ligand Complex for the Asymmetric [3+2] 1,3-Dipolar Cycloaddition of Azomethine Ylide with Malonates
  作者：Li Dai、Di Xu、Li-Wei Tang、Zhi-Ming Zhou

  DOI：10.1002/cctc.201403048

  日期：2015.4.7

  A series of enantioselective pyrrolidine‐2,4,4‐tricarboxylate derivatives were synthesized by the [3+2] 1,3‐dipolar cycloaddition of azomethine ylide with alkylidene malonates. By using 4 mol % of a CuIIN,P oxazolinylferrocene ligand complex and 10 mol % of a base, pyrrolidine analogues were obtained in high yields (77–99 %) and excellent enantioselectivities (up to 99 % ee).

  通过对亚甲亚胺叶立德与亚烷基丙二酸酯的[3 + 2] 1,3-偶极环加成反应，合成了一系列对映选择性吡咯烷-2,4,4-三羧酸酯衍生物。通过使用4 mol％的Cu IIN，P恶唑啉基二茂铁配体配合物和10 mol％的碱，可以高产率（77–99％）和优异的对映选择性（高达99％ee）获得吡咯烷类似物。
• Asymmetric [3+2] Cycloaddition of Azomethine Ylides Catalyzed by Silver(I) Triflate with a Chiral Bipyrrolidine-Derived Phosphine Ligand
  作者：Zhen-Jiang Xu、Chi-Ming Che、Xin Gu、Vanessa Lo

  DOI：10.1055/s-0032-1316779

  日期：——

  bipyrrolidine-derived phosphine ligands L1 and L2 were synthesized. The ‘AgOTf + L1’ protocol catalyzes the asymmetric [3+2] cycloaddition of azomethine ylides with alkenes to give highly substituted pyrrolidines in good yields (up to 90%) with moderate to high diastereoselectivities (up to >19:1 dr) and enantioselectivities (up to 76%). Two novel chiral bipyrrolidine-derived phosphine ligands L1 and L2 were synthesized

  摘要 合成了两个新颖的手性联吡咯烷衍生的膦配体L1和L2。“ AgOTf + L1 ”方案可催化偶氮甲亚胺与烯烃的不对称[3 + 2]环加成反应，以高收率（高达90％），中等至高非对映选择性（高达> 19：1 dr）提供高度取代的吡咯烷。对映选择性（高达76％）。 合成了两个新颖的手性联吡咯烷衍生的膦配体L1和L2。“ AgOTf + L1 ”方案可催化偶氮甲亚胺与烯烃的不对称[3 + 2]环加成反应，以高收率（高达90％），中等至高非对映选择性（高达> 19：1 dr）提供高度取代的吡咯烷。对映选择性（高达76％）。
• <i>exo</i>- and Enantioselective Cycloaddition of Azomethine Ylides Generated from <i>N</i>-Alkylidene Glycine Esters Using Chiral Phosphine−Copper Complexes
  作者：Yoji Oderaotoshi、Wenji Cheng、Shintaro Fujitomi、Yukihiro Kasano、Satoshi Minakata、Mitsuo Komatsu

  DOI：10.1021/ol036076s

  日期：2003.12.1

  High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first

  使用手性膦-铜配合物作为催化剂，由N-亚烷基甘氨酸酯与偶极亲和剂产生的偶氮甲碱的不对称1,3-偶极环加成反应具有很高的非对映选择性和对映选择性。尽管金属盐催化的甲亚胺烷基化物的环加成反应通常以内加合物为主要产物，但本方法是外选择性环加成反应的第一个例子。[反应：看文字]
• Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes
  作者：María Martín-Rodríguez、Luis M Castelló、Carmen Nájera、José M Sansano、Olatz Larrañaga、Abel de Cózar、Fernando P Cossío

  DOI：10.3762/bjoc.9.280

  日期：——

  The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S_a)-Binap·AuTFA]₂. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

  1,3-二极环加成反应是由二聚手性复合物[(Sa)-Binap·AuTFA]2高效催化的，该反应涉及甘氨酸衍生的氮内酯与马来酰亚胺的反应。丙氨酸衍生的氧代噁唑酮只与叔丁基丙烯酸酯发生反应，产生异常的区域化学反应，这一现象通过自然共振理论和核独立化学位移计算得到解释和支持。观察到的与马来酰亚胺和叔丁基丙烯酸酯的高对映选择性的起源是通过使用M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF)水平的密度泛函理论进行分析。描述了这些环加成产物在合成新的脯氨酸衍生物中的几种应用，这些衍生物具有2,5-trans排列，以及在制备复杂的融合多环分子中的应用。