methyl (E)-4-methylpent-2-enyl carbonate | 675608-08-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: methyl (E)-4-methylpent-2-enyl carbonate
• 英文别名: (E)-4-methylpent-2-enyl methyl carbonate；(2E)-4-methylpent-2-en-1-yl methyl carbonate；methyl [(E)-4-methylpent-2-enyl] carbonate
• CAS: 675608-08-9
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: ZUPQOXLKPRBUIX-SNAWJCMRSA-N

物化性质

• 沸点：
  176.9±19.0 °C(Predicted)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-4-methylpent-2-enyl carbonate 、 di(tert-butyl) imidodicarbonate lithium salt 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride chiral phosphoramidite-based ligand 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以42%的产率得到tert-butyl N-[(3R)-4-methylpent-1-en-3-yl]-N-[(2-methylpropan-2-yl)oxycarbonyl]carbamate
  参考文献：
  名称：

  对映选择性铱催化的氨的烯丙基胺化和方便的氨代用品。

  摘要：

  铱作为亲核试剂进行铱催化的不对称烯丙基化反应，并具有立体选择性，形成对称的二烯丙基胺，廉价的氨当量三氟乙酰胺钾或高反应性氨当量二叔丁基亚氨基二羧酸锂的相关烯丙基化反应形成了一系列易于保护的伯胺基，α-支链烯丙基胺的高收率，高支化至线性的区域选择性和高对映体过量。氨当量的反应用由含有单一立体化学元素的亚磷酰胺生成的催化剂进行。

  DOI：

  10.1021/ol701562p
• 作为产物：
  描述：

  (E)-4-methylpent-2-enal 在 吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 生成 methyl (E)-4-methylpent-2-enyl carbonate
  参考文献：
  名称：

  Effects of Catalyst Activation and Ligand Steric Properties on the Enantioselective Allylation of Amines and Phenoxides

  摘要：

  The yields, enantioselectivities, and regioselectivities of the reactions of amines and phenoxides with allylic carbonates in the presence of a metallacyclic iridium catalyst were compared. These data show that both preactivation of the catalyst and the size of the ligand affect the yield, enantioselectivity, and regioselectivity. With the activated catalyst containing a bis-naphthethylamino group, the allylic amination and etherification of a broad range of allylic carbonates occurred in high yields and with high regioselectivities and enantioselectivities.

  DOI：

  10.1021/ol050029d

文献信息

• Iridium-Catalyzed Asymmetric Allylic Amination with Polar Amines: Access to Building Blocks with Lead-Like Molecular Properties
  作者：Paolo Tosatti、Joachim Horn、Amanda J. Campbell、David House、Adam Nelson、Stephen P. Marsden

  DOI：10.1002/adsc.201000721

  日期：2010.12.17

  dimethyl sulfoxide (DMSO) allowed, for the first time, the systematic exploitation of highly polar, functionalized amines in asymmetric allylic substitutions: low molecular weight, sp3-rich chiral building blocks were obtained with physicochemical properties that will be valuable in the synthesis of lead-like small molecules.

  空气稳定的铱催化剂和偶极非质子传递溶剂二甲基亚砜（DMSO）的组合首次允许在不对称的烯丙基取代中系统性地利用高极性，官能化的胺：低分子量，富含sp 3的手性体系获得具有理化性质的嵌段，这对于合成铅样小分子将是有价值的。
• Enantioselective Allylation of Aromatic Amines after In Situ Generation of an Activated Cyclometalated Iridium Catalyst
  作者：Chutian Shu、Andreas Leitner、John F. Hartwig

  DOI：10.1002/anie.200460276

  日期：2004.9.13
• US4450285A
  申请人：——

  公开号：US4450285A

  公开（公告）日：1984-05-22
• US7732365B2
  申请人：——

  公开号：US7732365B2

  公开（公告）日：2010-06-08
• Effects of Catalyst Activation and Ligand Steric Properties on the Enantioselective Allylation of Amines and Phenoxides
  作者：Andreas Leitner、Chutian Shu、John F. Hartwig

  DOI：10.1021/ol050029d

  日期：2005.3.1

  The yields, enantioselectivities, and regioselectivities of the reactions of amines and phenoxides with allylic carbonates in the presence of a metallacyclic iridium catalyst were compared. These data show that both preactivation of the catalyst and the size of the ligand affect the yield, enantioselectivity, and regioselectivity. With the activated catalyst containing a bis-naphthethylamino group, the allylic amination and etherification of a broad range of allylic carbonates occurred in high yields and with high regioselectivities and enantioselectivities.