but-3-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 1048703-34-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: but-3-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 1048703-34-9
• 化学式: C₁₂H₂₁NO₃
• 分子量: 227.304
• InChiKey: LLDQAONAQGHHMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  but-3-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 、 对溴甲苯 在 仲丁基锂 、 鹰爪豆碱 、 zinc diacetate 、 tris-(dibenzylideneacetone)dipalladium(0) 、 2-二环己基磷-2',6'-二异丙氧基-1,1'-联苯 作用下， 以 乙醚 、 正己烷 、 四氢呋喃 、 甲苯 为溶剂， 反应 24.0h， 以76%的产率得到(R)-(+)-1-(p-tolyl)but-3-en-1-yl 2,2,4,4-tetramethyloxazolidine-3-carboxylate
  参考文献：
  名称：

  Enantioselective α-Arylation of O-Carbamates via Sparteine-Mediated Lithiation and Negishi Cross-Coupling

  摘要：

  A general and enantioselective arylation of carbamates derived from primary alcohols was developed by combining Hoppe's sparteine-mediated asymmetric lithiation with Negishi cross-coupling. Coupled with Aggarwal's lithiation-borylation sequence, the current method provides a short and divergent access to a variety of enantioenriched secondary and tertiary benzylic alcohols.

  DOI：

  10.1021/acs.orglett.6b03472
• 作为产物：
  描述：

  2,2,4,4-四甲基-1,3-恶唑烷 在 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 mineral oil 、 苯 为溶剂， 反应 32.5h， 生成 but-3-enyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  Enantioselective α-Arylation of O-Carbamates via Sparteine-Mediated Lithiation and Negishi Cross-Coupling

  摘要：

  A general and enantioselective arylation of carbamates derived from primary alcohols was developed by combining Hoppe's sparteine-mediated asymmetric lithiation with Negishi cross-coupling. Coupled with Aggarwal's lithiation-borylation sequence, the current method provides a short and divergent access to a variety of enantioenriched secondary and tertiary benzylic alcohols.

  DOI：

  10.1021/acs.orglett.6b03472

文献信息

• Pd-catalyzed γ-arylation of γ,δ-unsaturated <i>O</i>-carbamates <i>via</i> an unusual haptotropic rearrangement
  作者：Titouan Royal、Olivier Baudoin

  DOI：10.1039/c8sc05058a

  日期：——

  An unusual γ-selectivity was observed in the arylation of γ,δ-unsaturated O-carbamates involving directed lithiation, transmetallation to zinc and Negishi coupling, when a specific combination of aryl electrophile and phosphine ligand is employed. Mechanistic studies indicate that an unusual, stereospecific haptotropic rearrangement of the palladium–diene intermediate is involved.

  当使用芳基亲电子试剂和膦配体的特定组合时，在γ,δ-不饱和O-氨基甲酸酯的芳基化中观察到不寻常的γ-选择性，涉及直接锂化、锌的金属转移和Negishi偶联。机理研究表明，其中涉及钯-二烯中间体的不寻常的立体特异性触合重排。
• Determination of the Effect of Cation−π Interactions on the Stability of α-Oxy-Organolithium Compounds
  作者：Pablo Monje、M. Rita Paleo、Luis García-Río、F. Javier Sardina

  DOI：10.1021/jo801176d

  日期：2008.9.19

  Sn-Li exchange equilibria have allowed the quantification of the stabilizing effect of cation-pi interactions in organolithium chemistry. Stabilization energy data on the effect of Li-pi complexation of an aromatic ring or a C=C double bond in organolithium compounds are presented. The amount of stabilization gained by complexation of the Li atom with a pi system in alpha-oxy-organolithium compounds is quite comparable to the one observed in systems containing Li-N or Li-O interactions.