(3R)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-4-methylpent-1-ene

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (3R)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-4-methylpent-1-ene
• 英文别名: CH2CHCH(isopropyl)BO2(C(CH3)2)2；4,4,5,5-tetramethyl-2-[(3R)-4-methylpent-1-en-3-yl]-1,3,2-dioxaborolane
• 化学式: C₁₂H₂₃BO₂
• 分子量: 210.124
• InChiKey: ZIFKTLLUMRIEHF-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-4-methylpent-1-ene 、 苯甲醛 在 正丁基锂 、 三氟乙酸酐 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 16.75h， 以94%的产率得到(1S,3E)-5-methyl-1-phenylhex-3-en-1-ol
  参考文献：
  名称：

  Highly Diastereo- and Enantioselective Allylboration of Aldehydes using α-Substituted Allyl/Crotyl Pinacol Boronic Esters via in Situ Generated Borinic Esters

  摘要：

  Readily available, alpha-substituted allyl/crotyl pinacol boronic esters often give low E/Z selectivity (with Z favored) in reactions with aldehydes. We found that addition of nBuLi to the pinacol boronic ester followed by trapping of the alkoxide with TFAA leads to an intermediate allyl borinic ester which undergoes allylboration with very high E selectivity. The substrate scope includes primary to tertiary alkyl alpha-substituents, crotyl substrates, and the previously unreported beta-methallyl pinacol boronic esters. The latter give very high Z selectivity under standard conditions which is completely reversed to high E selectivity under the new conditions. Monitoring the reaction by B-11 NMR confirmed that the reaction proceeds through a borinic ester intermediate.

  DOI：

  10.1021/ja401564z
• 作为产物：
  描述：

  2-chloromethylvinylboronic acid pinacol ester 、 异丙基溴化镁 在 C₄H₃S(2-CO₂Cu) 、 (S,S)-((S)-C₂₀H₁₂O₂)PN(CH(CH₃)C₆H₄(o-OCH₃))2 作用下， 以 二氯甲烷 为溶剂， 生成 (3R)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-4-methylpent-1-ene
  参考文献：
  名称：

  α-取代的烯丙基硼酸酯的催化对映选择性制备：向功能化醛中一锅加成，以及制备手性烯丙基三氟硼酸酯试剂的途径。

  摘要：

  DOI：

  10.1002/anie.200700975

文献信息

• Catalytic Enantioselective Preparation of α-Substituted Allylboronates: One-Pot Addition to Functionalized Aldehydes and a Route to Chiral Allylic Trifluoroborate Reagents
  作者：Lisa Carosi、Dennis G. Hall

  DOI：10.1002/anie.200700975

  日期：2007.8.3
• Highly Diastereo- and Enantioselective Allylboration of Aldehydes using α-Substituted Allyl/Crotyl Pinacol Boronic Esters via in Situ Generated Borinic Esters
  作者：Jack L.-Y. Chen、Helen K. Scott、Matthew J. Hesse、Christine L. Willis、Varinder K. Aggarwal

  DOI：10.1021/ja401564z

  日期：2013.4.10

  Readily available, alpha-substituted allyl/crotyl pinacol boronic esters often give low E/Z selectivity (with Z favored) in reactions with aldehydes. We found that addition of nBuLi to the pinacol boronic ester followed by trapping of the alkoxide with TFAA leads to an intermediate allyl borinic ester which undergoes allylboration with very high E selectivity. The substrate scope includes primary to tertiary alkyl alpha-substituents, crotyl substrates, and the previously unreported beta-methallyl pinacol boronic esters. The latter give very high Z selectivity under standard conditions which is completely reversed to high E selectivity under the new conditions. Monitoring the reaction by B-11 NMR confirmed that the reaction proceeds through a borinic ester intermediate.

表征谱图