methyl (2E)-7-nitroocta-2,7-dienoate | 201672-56-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2E)-7-nitroocta-2,7-dienoate
• CAS: 201672-56-2
• 化学式: C₉H₁₃NO₄
• 分子量: 199.207
• InChiKey: NRFDAWDBOOMBOE-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲铝双(2,6-二叔丁基-4-苯甲醚) 、 methyl (2E)-7-nitroocta-2,7-dienoate 在 乙烯基正丁醚 作用下， 生成 Methyl 2-[2-[(3,5-ditert-butyl-1-methyl-4-oxocyclohexa-2,5-dien-1-yl)methyl]-2-nitrocyclopentyl]acetate 、 methyl (E)-8-(3,5-ditert-butyl-1-methyl-4-oxocyclohexa-2,5-dien-1-yl)-7-nitrooct-2-enoate
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 17. The Spiro Mode. Efficient and Highly Selective Synthesis of Azapropellanes

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloaddition has been developed. Intermolecular [4 + 2] cycloaddition of a 2-nitroalkene (bearing an unsaturated ester moiety, the dipolarophile) with a vinyl ether produces a cyclic nitronate substituted at C(3) wherein the only stereogenic center is the anomeric carbon C(6). Since the dipolarophile is attached to a tether extending from the C(3) of the nitronate (a-carbon of the nitroalkene), the intramolecular [3 + 2] cycloaddition affords a spiro tricyclic nitroso acetal. The cycloaddition proceeds smoothly for three- and four-atom tethers to afford five- and six-membered rings. Both E- and Z-unsaturated esters serve well as dipolarophiles, but the E-isomers react more selectively. Hydrogenolysis of the nitroso acetals affords the spiro tricyclic alpha-hydroxy lactams in good yield. Remarkably high levels of asymmetric induction are observed with the use of a chiral vinyl ether derived from (1R,2S)-2-phenylcyclohexanol. The origin of asymmetric induction is a combination of the established face selectivity of the enol ether and the preference for a distal fold of the tether away from the: substituent on the anomeric carbon. The scope and limitations of this transformation and an analysis of the origin of stereoselectivity are provided.

  DOI：

  10.1021/jo9719057
• 作为产物：
  描述：

  (E)-7-氧代庚-2-烯酸甲酯 在 正丁基锂 、 mercury(II) perchlorate 、 三乙胺 、 sodium nitrite 作用下， 反应 27.33h， 生成 methyl (2E)-7-nitroocta-2,7-dienoate
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 17. The Spiro Mode. Efficient and Highly Selective Synthesis of Azapropellanes

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloaddition has been developed. Intermolecular [4 + 2] cycloaddition of a 2-nitroalkene (bearing an unsaturated ester moiety, the dipolarophile) with a vinyl ether produces a cyclic nitronate substituted at C(3) wherein the only stereogenic center is the anomeric carbon C(6). Since the dipolarophile is attached to a tether extending from the C(3) of the nitronate (a-carbon of the nitroalkene), the intramolecular [3 + 2] cycloaddition affords a spiro tricyclic nitroso acetal. The cycloaddition proceeds smoothly for three- and four-atom tethers to afford five- and six-membered rings. Both E- and Z-unsaturated esters serve well as dipolarophiles, but the E-isomers react more selectively. Hydrogenolysis of the nitroso acetals affords the spiro tricyclic alpha-hydroxy lactams in good yield. Remarkably high levels of asymmetric induction are observed with the use of a chiral vinyl ether derived from (1R,2S)-2-phenylcyclohexanol. The origin of asymmetric induction is a combination of the established face selectivity of the enol ether and the preference for a distal fold of the tether away from the: substituent on the anomeric carbon. The scope and limitations of this transformation and an analysis of the origin of stereoselectivity are provided.

  DOI：

  10.1021/jo9719057

文献信息

• Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 17. The Spiro Mode. Efficient and Highly Selective Synthesis of Azapropellanes
  作者：Scott E. Denmark、Donald S. Middleton

  DOI：10.1021/jo9719057

  日期：1998.3.1

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloaddition has been developed. Intermolecular [4 + 2] cycloaddition of a 2-nitroalkene (bearing an unsaturated ester moiety, the dipolarophile) with a vinyl ether produces a cyclic nitronate substituted at C(3) wherein the only stereogenic center is the anomeric carbon C(6). Since the dipolarophile is attached to a tether extending from the C(3) of the nitronate (a-carbon of the nitroalkene), the intramolecular [3 + 2] cycloaddition affords a spiro tricyclic nitroso acetal. The cycloaddition proceeds smoothly for three- and four-atom tethers to afford five- and six-membered rings. Both E- and Z-unsaturated esters serve well as dipolarophiles, but the E-isomers react more selectively. Hydrogenolysis of the nitroso acetals affords the spiro tricyclic alpha-hydroxy lactams in good yield. Remarkably high levels of asymmetric induction are observed with the use of a chiral vinyl ether derived from (1R,2S)-2-phenylcyclohexanol. The origin of asymmetric induction is a combination of the established face selectivity of the enol ether and the preference for a distal fold of the tether away from the: substituent on the anomeric carbon. The scope and limitations of this transformation and an analysis of the origin of stereoselectivity are provided.