α-diazo diallyl-tert-butylphosphonoacetate | 222174-25-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: α-diazo diallyl-tert-butylphosphonoacetate
• 英文别名: Tert-butyl 2-bis(prop-2-enoxy)phosphoryl-2-diazoacetate；tert-butyl 2-bis(prop-2-enoxy)phosphoryl-2-diazoacetate
• CAS: 222174-25-6
• 化学式: C₁₂H₁₉N₂O₅P
• 分子量: 302.267
• InChiKey: DTAYTJVICBIRFC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  63.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  α-diazo diallyl-tert-butylphosphonoacetate 在 dirhodium tetraacetate 、 甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 生成
  参考文献：
  名称：

  Double Diastereoselective Intramolecular Cyclopropanation to P-Chiral [3.1.0]-Bicyclic Phosphonates

  摘要：

  [GRAPHICS]A double diastereotopic differentiation strategy on a phosphonoacetate template is described. The approach utilizes Rh-2(OAC)(4)-catalyzed intramolecular cyclopropanation (ICP) employing the (R)-pantolactone auxiliary in the ester functionality of the phosphonoacetate. The olefinic diastereofacial selectivity is governed by inherent electronic and steric interactions in the reacting carbene intermediate, while the group selectivity is dictated by the chiral auxiliary. This approach is being developed as an effective method to access bicyclic P-chiral phosphonates.

  DOI：

  10.1021/ol026080o
• 作为产物：
  描述：

  氯乙酸叔丁酯 在 对甲苯磺酰叠氮 、 potassium tert-butylate 、 potassium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 α-diazo diallyl-tert-butylphosphonoacetate
  参考文献：
  名称：

  Double Diastereoselective Intramolecular Cyclopropanation to P-Chiral [3.1.0]-Bicyclic Phosphonates

  摘要：

  [GRAPHICS]A double diastereotopic differentiation strategy on a phosphonoacetate template is described. The approach utilizes Rh-2(OAC)(4)-catalyzed intramolecular cyclopropanation (ICP) employing the (R)-pantolactone auxiliary in the ester functionality of the phosphonoacetate. The olefinic diastereofacial selectivity is governed by inherent electronic and steric interactions in the reacting carbene intermediate, while the group selectivity is dictated by the chiral auxiliary. This approach is being developed as an effective method to access bicyclic P-chiral phosphonates.

  DOI：

  10.1021/ol026080o

文献信息

• Intramolecular cyclopropanation reactions en route to novel P-heterocycles
  作者：Paul R. Hanson、Kevin T. Sprott、Aaron D. Wrobleski

  DOI：10.1016/s0040-4039(99)00023-4

  日期：1999.2

  The first examples of intramolecular cyclopropanation reactions on a phosphonate template catalyzed by Rh-2(OAc)(4) are described. These reactions proceed in excellent yield and give mixtures of the P-heterocycles cis-2a-d and trans-2a-d with moderate levels of diastereoselectivity. The diastereoselectivity of this transformation is dependent upon the size of the alkyl group R contained in the alkyl alpha-diazodiallylphosphonoacetate starting materials 1a-d. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Conformationally Constrained α-Boc-Aminophosphonates via Transition Metal-Catalyzed/Curtius Rearrangement Strategies
  作者：Joel D. Moore、Kevin T. Sprott、Paul R. Hanson

  DOI：10.1021/jo0262208

  日期：2002.11.1

  A transition metal-catalyzed/Curtius rearrangement sequence toward the development of conformationally constrained alpha-Boc-aminophosphonates 2-6 is described. An approach using the versatile tert-butylphosphonoacetate moieties 1a and 1b to derive an array of mono- and bicyclic alpha-Boc-aminophosphonate systems is presented. Conformational constraint is incorporated using either the ring-closing metathesis reaction catalyzed by the first generation Grubbs catalyst or intramolecular cyclopropanation mediated by Rh-2(OAc)(4). Using the tert-butyl ester functionality in 1a or 1b as a potential amino group, the Curtius rearrangement provides an efficient route toward the target alpha-Boc-aminophosphonates.
• Double Diastereoselective Intramolecular Cyclopropanation to <i>P</i>-Chiral [3.1.0]-Bicyclic Phosphonates
  作者：Joel D. Moore、Kevin T. Sprott、Aaron D. Wrobleski、Paul R. Hanson

  DOI：10.1021/ol026080o

  日期：2002.7.1

  [GRAPHICS]A double diastereotopic differentiation strategy on a phosphonoacetate template is described. The approach utilizes Rh-2(OAC)(4)-catalyzed intramolecular cyclopropanation (ICP) employing the (R)-pantolactone auxiliary in the ester functionality of the phosphonoacetate. The olefinic diastereofacial selectivity is governed by inherent electronic and steric interactions in the reacting carbene intermediate, while the group selectivity is dictated by the chiral auxiliary. This approach is being developed as an effective method to access bicyclic P-chiral phosphonates.