2-Diazo-3-oxo-4,4-diphenyl-pentanoic acid methyl ester | 164072-96-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-Diazo-3-oxo-4,4-diphenyl-pentanoic acid methyl ester
• 英文别名: methyl (2Z)-2-diazo-3-oxo-4,4-diphenylpentanoate
• CAS: 164072-96-2
• 化学式: C₁₈H₁₆N₂O₃
• 分子量: 308.337
• InChiKey: RGCKVXRXWPULQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Diazo-3-oxo-4,4-diphenyl-pentanoic acid methyl ester 在 dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate] bis(ethyl acetate) 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以70%的产率得到3-Methyl-2-oxo-3-phenyl-indan-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate]: an exceptionally effective Rh(II) catalyst for enantiotopically selective aromatic C–H insertions of diazo ketoesters

  摘要：

  Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh-2[(S)-TFPTTL](4), in which the phthalimido hydrogen atoms of the parent dirhodium(II) complex are substituted by fluorine atoms, dramatically enhances the reactivity and enantioselectivity (up to 97% ee) in intramolecular aromatic C-H insertion reactions of methyl 4-alkyl-2-diazo-4,4-diphenyl-3-oxopropionates. Catalysis with the use of 0.001 mol% of Rh-2[(S)-TFPTTL](4) has achieved the highest turnover number (up to 98,000 with the methyl substituent) ever recorded for chiral dirhodium(II) complex-catalyzed carbene transformations, without compromising the yield or enantioselectivity of the process. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00075-2
• 作为产物：
  描述：

  2,2-二苯基丙酸 在 氯化亚砜 、 三乙胺 、 N,N-二甲基甲酰胺 、 甲烷磺酰基叠氮化物 作用下， 以 四氢呋喃 、 甲苯 、 乙腈 为溶剂， 生成 2-Diazo-3-oxo-4,4-diphenyl-pentanoic acid methyl ester
  参考文献：
  名称：

  Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate]: an exceptionally effective Rh(II) catalyst for enantiotopically selective aromatic C–H insertions of diazo ketoesters

  摘要：

  Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh-2[(S)-TFPTTL](4), in which the phthalimido hydrogen atoms of the parent dirhodium(II) complex are substituted by fluorine atoms, dramatically enhances the reactivity and enantioselectivity (up to 97% ee) in intramolecular aromatic C-H insertion reactions of methyl 4-alkyl-2-diazo-4,4-diphenyl-3-oxopropionates. Catalysis with the use of 0.001 mol% of Rh-2[(S)-TFPTTL](4) has achieved the highest turnover number (up to 98,000 with the methyl substituent) ever recorded for chiral dirhodium(II) complex-catalyzed carbene transformations, without compromising the yield or enantioselectivity of the process. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00075-2

文献信息

• A Polymer-Supported Chiral Dirhodium(II) Complex: Highly Durable and Recyclable Catalyst for Asymmetric Intramolecular CH Insertion Reactions
  作者：Koji Takeda、Tadashi Oohara、Masahiro Anada、Hisanori Nambu、Shunichi Hashimoto

  DOI：10.1002/anie.201003730

  日期：2010.9.17

  A highly effective immobilization of [Rh2(S‐PTTL)4] (PTTL=N‐phthaloyl‐tert‐leucinate) has been achieved by copolymerization of monomer 1 with styrene and a flexible cross‐linker. The immobilized catalyst promoted the title reaction at −78 °C with high enantioselectivity, and could be used for up to 100 cycles with a low level of leaching (0.28 ppm).

  通过单体1与苯乙烯和柔性交联剂的共聚，已实现了[Rh 2（S -PTTL）4 ]（PTTL = N-邻苯二甲酰叔亮氨酸）的高效固定。固定化的催化剂在-78°C下以高对映选择性促进了标题反应，可在低浸出（0.28 ppm）的条件下用于多达100个循环。
• Universal Strategy for the Immobilization of Chiral Dirhodium Catalysts
  作者：Huw M. L. Davies、Abbas M. Walji

  DOI：10.1021/ol0508835

  日期：2005.7.1

  [reaction: see text] Chiral rhodium(II) catalysts used in asymmetric carbenoid chemistry can be efficiently heterogenized using a novel immobilization strategy. The immobilized catalysts display similar reactivity and stereoselectivity to their homogeneous counterparts and can be effectively recycled with limited loss in stereoselectivity.

  [反应：参见正文]使用新型固定化策略可以有效地异质化不对称类胡萝卜素化学中使用的手性铑（II）催化剂。固定化催化剂显示出与其均相同类催化剂相似的反应性和立体选择性，并且可以有效地循环利用，而立体选择性的损失有限。
• Asymmetric creation of quaternary carbon centers by enantiotopically selective aromatic C-H insertion catalyzed by chiral dirhodium(II) car☐ylates
  作者：Nobuhide Watanabe、Yoshihito Ohtake、Shun-ichi Hashimoto、Motoo Shiro、Shiro Ikegami

  DOI：10.1016/0040-4039(95)00067-m

  日期：1995.2

  C-H insertion reactions of α-diazo ketones catalyzed by dirhodium(II) tetrakis[N-phthaloyl-(S)-phenylalaninate], leading to the formation of (S)-1-alkyl-1-phenyl-2-indanones containing a chiral quaternary carbon atom with up to 95% ee.

  对四苯[II]-[N-邻苯二甲酰基-[S]-苯丙氨酸]催化α-重氮酮的分子内芳族CH插入反应，实现了对位苯环的高度分化。含有手性季碳原子和ee高达95％的-1-烷基-1-苯基-2-茚满酮。
• POLYMER-SUPPORTED METAL COMPLEX CATALYST
  申请人：Hashimoto Shunichi

  公开号：US20090227743A1

  公开（公告）日：2009-09-10

  The present invention relates to a polymer-supported rhodium (II) catalyst and its application, which includes addition reaction to carbon-carbon multiple bond in α-diazocarbonyl compounds, insertion reaction to C—H and X—H (X═N, O, S, Se, Si and the like) bonds, or rearrangement and additional cyclization reaction thereof A novel insoluble polymer-supported rhodium (II) complex was prepared through a ligand exchange reaction between an insoluble polymer and a rhodium (II) carboxylato complex, wherein the insoluble polymer was prepared by a copolymerization reaction of (i) a styrene derivative with substituted carboxylic acid, (ii) a stylene, and (iii) a linear alkane with both ends substituted by vinylbenzyloxy groups, Namely, a polymer-supported metal complex catalyst having the following chemical formula 1: wherein M 1 and M 2 are rhodium, and the like; and X is an oxygen atom, etc; and R 4 is an alkyl group, and the like; and k is 1 to 15%, m is 1 to 5% relative to k+l+m, and l is the remainder; and n is 4 and others; and R 1 is alkyl-2-(4′-alkyloxy phthalimido methyl), etc, R 2 is phenyl, etc; R 3 is 4,4′-(1,3-propyrene-1,3-dioxymethyl)phenyl, etc.

  本发明涉及一种聚合物支撑的二价铑催化剂及其应用，包括对α-重氮基化合物中的碳-碳多键进行加成反应，对C-H和X-H（其中X = N，O，S，Se，Si等）键进行插入反应，或对其进行重排和附加环化反应。通过不溶性聚合物与二价铑羧酸酯配合物之间的配体交换反应制备了一种新型不溶性聚合物支撑的铑（II）配合物，其中不溶性聚合物是由（i）一种苯乙烯衍生物与取代羧酸、（ii）一种苯乙烯和（iii）两端取代为乙烯基苯甲氧基基团的线性烷烃进行共聚反应制备的。即，具有以下化学式1的聚合物支撑金属配合物催化剂：其中M1和M2是铑等；X是氧原子等；R4是烷基等；k相对于k+l+m为1至15％，m为1至5％，l为余数；n为4等；R1是烷基-2-（4'-烷氧基邻苯二酰亚甲基）等，R2是苯基等；R3是4,4'-（1,3-丙烯-1,3-二氧甲基）苯基等。
• US8092720B2
  申请人：——

  公开号：US8092720B2

  公开（公告）日：2012-01-10