tert-Butyl (S)-(-)-2-allyl-2-methylacetoacetate | 130203-09-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: tert-Butyl (S)-(-)-2-allyl-2-methylacetoacetate
• 英文别名: tert-Butyl (S)-(-)-2-allyl-2-methylacetatoacetate；tert-butyl 2-acetyl-2-methylpent-4-enoate；tert-butyl (2S)-2-acetyl-2-methylpent-4-enoate
• CAS: 130203-09-7
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: FGEIAPCEJYVVIW-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-Butyl (S)-(-)-2-allyl-2-methylacetoacetate 在 吡啶 、 lithium aluminium tetrahydride 、 jones reagent 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 4.17h， 生成 (S)-(-)-2-Acetyl-2-methyl-4-pentenyl benzoate
  参考文献：
  名称：

  Asymmetric induction reactions. IV. Palladium-catalyzed asymmetric allylations of chiral enamines bearing phosphine groups.

  摘要：

  钯催化的手性烯胺的不对称烯基化反应，源自(S)-2-(二苯膦甲基)吡咯烷，产生了光学活性α-烯基羰基化合物，并且光学产率很高。手性烯胺中的磷基团在这些钯催化反应中很可能作为手性配体。在与分子内磷烷基团配位的π-烯基钯配合物的过渡态中，阴离子对应物或烯基化试剂被认为在控制对映选择性的等级方面起着重要作用。

  DOI：

  10.1248/cpb.39.616
• 作为产物：
  描述：

  2-甲基-3-氧代丁酸叔丁酯 在 四(三苯基膦)钯 sodium acetate 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 24.0h， 生成 tert-Butyl (S)-(-)-2-allyl-2-methylacetoacetate
  参考文献：
  名称：

  Asymmetric induction reactions. IV. Palladium-catalyzed asymmetric allylations of chiral enamines bearing phosphine groups.

  摘要：

  钯催化的手性烯胺的不对称烯基化反应，源自(S)-2-(二苯膦甲基)吡咯烷，产生了光学活性α-烯基羰基化合物，并且光学产率很高。手性烯胺中的磷基团在这些钯催化反应中很可能作为手性配体。在与分子内磷烷基团配位的π-烯基钯配合物的过渡态中，阴离子对应物或烯基化试剂被认为在控制对映选择性的等级方面起着重要作用。

  DOI：

  10.1248/cpb.39.616

文献信息

• Chiral Primary Amine/Palladium Dual Catalysis for Asymmetric Allylic Alkylation of β-Ketocarbonyl Compounds with Allylic Alcohols
  作者：Han Zhou、Long Zhang、Changming Xu、Sanzhong Luo

  DOI：10.1002/anie.201505946

  日期：2015.10.19

  promote the direct asymmetric allylic alkylation (AAA) of β‐ketocarbonyl compounds. In particular, the synergistic dual catalytic system enabled the AAA reaction of challenging acyclic aliphatic ketones, such as β‐ketocarbonyl compounds and 1,3‐diketones.

  开发了由手性伯胺和钯配合物组成的高效双催化体系，以促进β-酮羰基化合物的直接不对称烯丙基烷基化（AAA）。特别是，协同双催化系统使具有挑战性的无环脂肪族酮（例如β-酮羰基化合物和1,3-二酮）能够进行AAA反应。
• π-Coordinating Chiral Primary Amine/Palladium Synergistic Catalysis for Asymmetric Allylic Alkylation
  作者：Yaning Wang、Junli Chai、Chang You、Jie Zhang、Xueling Mi、Long Zhang、Sanzhong Luo

  DOI：10.1021/jacs.9b13026

  日期：2020.2.12

  synergistic catalysis for asymmetric allylic alkylation of α-branched β-ketocarbonyls. The use of arene-containing chiral primary amine catalyst led to not only enhanced reaction rate but also reversed chiral induction comparing with its sterically bulky derivative. Both enantiomers of the allylic adducts bearing acyclic all-carbon quaternary stereocenters could be obtained from the same configured chiral aminocatalyst

  我们报告了一种含芳烃的手性伯胺作为双氨基催化剂和配体。用于α-支化β-酮羰基不对称烯丙基烷基化的π-配位氨基催化剂/钯协同催化。与空间庞大的衍生物相比，含芳烃的手性伯胺催化剂的使用不仅提高了反应速率，而且还逆转了手性诱导。带有无环全碳四元立体中心的烯丙基加合物的两种对映异构体都可以从相同配置的手性氨基催化剂中以高效和优异的区域选择性、立体选择性和对映选择性获得。机理研究揭示了一种独特的 Pd-芳烃 π 配位模式，用于有效催化。
• Asymmetric induction reactions. V. The palladium-catalyzed asymmetric .alpha.-allylation of carbonyl compounds with chiral allyl esters via enamines and imines
  作者：Kunio Hiroi、Jun Abe、Kyoko Suya、Shuko Sato、Toshihiro Koyama

  DOI：10.1021/jo00080a033

  日期：1994.1

  A novel and excellent method for asymmetric alpha-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl eaters has been developed. Readily available chiral allyl eaters having chirality at the alpha-position of the eater carbonyl group, such as (S)-proline and other (S)-alpha-amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding alpha-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.
• Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst
  作者：Kazuhiro Nagata、Daisuke Sano、Yu Shimizu、Michiko Miyazaki、Takuya Kanemitsu、Takashi Itoh

  DOI：10.1016/j.tetasy.2009.10.018

  日期：2009.11

  The catalytic asymmetric alkylation of alpha-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a beta-lactam derivative were synthesized. (C) 2009 Elsevier Ltd. All rights reserved.
• Palladium-catalyzed asymmetric allylations of chiral enamines bearing phosphine functionality. Effects of anionic counterparts of allylating reagents on asymmetric induction
  作者：Kunio Hiroi、Jun Abe

  DOI：10.1016/s0040-4039(00)94460-5

  日期：1990.1