trans-1-methoxy-2-(3-methyl-octa-2,7-dienyl)-benzene | 757188-19-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: trans-1-methoxy-2-(3-methyl-octa-2,7-dienyl)-benzene
• 英文别名: 1-methoxy-2-[(2E)-3-methylocta-2,7-dienyl]benzene
• CAS: 757188-19-5
• 化学式: C₁₆H₂₂O
• 分子量: 230.35
• InChiKey: ZANOUDXDOCBETD-WYMLVPIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-1-methoxy-2-(3-methyl-octa-2,7-dienyl)-benzene 在 (dppm)PtI₂ 、 PMe₃, AgBF₄ 作用下， 以 硝基甲烷 为溶剂， 反应 3.0h， 以86%的产率得到C₁₆H₂₂O
  参考文献：
  名称：

  Modular Catalysts for Diene Cycloisomerization:  Rapid and Enantioselective Variants for Bicyclopropane Synthesis

  摘要：

  Deconstructing the tridentate (triphos)Pt(II) first-generation catalysts into mixed diphosphine/monophosphine combinations (P2P) has led to new, more active catalysts for the cycloisomerization of 1,6-, and 1,7-dienes into bicyclo-[3.1.0] and -[4.1.0] products. When the diphosphine was the small bite angle dppm, reaction rates were similar to 20-fold faster than with triphos, although reaction rates and diastereoselectivities were also sensitive to the monophosphine (PMe3 being optimal for rate, PPh3 being optimal for selectivity). When the diphosphine was xyl-BINAP or SEGPHOS, the catalysts were enantioselective, and enantio-ratios up to 98:2 were observed. Both sets of catalysts showed enhanced functional group tolerance in comparison to the original (triphos)Pt2+ catalyst. X-ray structures for both precatalysts are also reported.

  DOI：

  10.1021/ja064335d
• 作为产物：
  描述：

  1-庚烯-6-炔 、 2-甲氧基溴苄 、 三甲基铝 在 四(三苯基膦)钯 二氯二茂锆 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 48.17h， 以78%的产率得到trans-1-methoxy-2-(3-methyl-octa-2,7-dienyl)-benzene
  参考文献：
  名称：

  Platinum(II)-Catalyzed 1,6-Diene Cycloisomerizations:  Turnover in the Absence of β-Hydride Elimination

  摘要：

  Electrophilic pincer-ligated Pt(II)-clications are efficient catalysts for the cycloisomerization of 1,6-dienes, initiated by alkene activation. The tridentate ligands inhibit beta-hydride elimination and thus enable cationic mechanisms that turnover by Pt(II) extrusion. PPP ligands lead to cyclopropane products, while PNP ligands provide cyclohexene products; mechanistic issues are also discussed.

  DOI：

  10.1021/ol048780u

文献信息

• Modular Catalysts for Diene Cycloisomerization:  Rapid and Enantioselective Variants for Bicyclopropane Synthesis
  作者：Jeremy A. Feducia、Alison N. Campbell、Michael Q. Doherty、Michel R. Gagné

  DOI：10.1021/ja064335d

  日期：2006.10.1

  Deconstructing the tridentate (triphos)Pt(II) first-generation catalysts into mixed diphosphine/monophosphine combinations (P2P) has led to new, more active catalysts for the cycloisomerization of 1,6-, and 1,7-dienes into bicyclo-[3.1.0] and -[4.1.0] products. When the diphosphine was the small bite angle dppm, reaction rates were similar to 20-fold faster than with triphos, although reaction rates and diastereoselectivities were also sensitive to the monophosphine (PMe3 being optimal for rate, PPh3 being optimal for selectivity). When the diphosphine was xyl-BINAP or SEGPHOS, the catalysts were enantioselective, and enantio-ratios up to 98:2 were observed. Both sets of catalysts showed enhanced functional group tolerance in comparison to the original (triphos)Pt2+ catalyst. X-ray structures for both precatalysts are also reported.
• Platinum(II)-Catalyzed 1,6-Diene Cycloisomerizations:  Turnover in the Absence of β-Hydride Elimination
  作者：William D. Kerber、Jeong Hwan Koh、Michel R. Gagné

  DOI：10.1021/ol048780u

  日期：2004.8.1

  Electrophilic pincer-ligated Pt(II)-clications are efficient catalysts for the cycloisomerization of 1,6-dienes, initiated by alkene activation. The tridentate ligands inhibit beta-hydride elimination and thus enable cationic mechanisms that turnover by Pt(II) extrusion. PPP ligands lead to cyclopropane products, while PNP ligands provide cyclohexene products; mechanistic issues are also discussed.