(3R,4R)-5-((tert-butyldiphenylsilyl)oxy)-3-methoxy-4-methylpentanal | 166322-45-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3R,4R)-5-((tert-butyldiphenylsilyl)oxy)-3-methoxy-4-methylpentanal
• CAS: 166322-45-8
• 化学式: C₂₃H₃₂O₃Si
• 分子量: 384.591
• InChiKey: MIQXPGIEMIWVHM-DENIHFKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  27.0
• 可旋转键数：
  9.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3R,4R)-5-((tert-butyldiphenylsilyl)oxy)-3-methoxy-4-methylpentanal 、 以71%的产率得到(3S,4R,6R,7R,E)-8-((tert-butyldiphenylsilyl)oxy)-1-(dimethyl(phenyl)silyl)-6-methoxy-3,7-dimethyloct-1-en-4-ol
  参考文献：
  名称：

  Enantiodivergent hydroboration reactions of a racemic allenylsilane with diisopinocampheylborane and Curtin–Hammett controlled double asymmetric crotylboration reactions of (S)-E-α-phenyldimethylsilyl(ddiisopinocampheyl)-crotylborane

  摘要：

  The enantiodivergent hydroboration reactions of racemic allenylsilane (+/-)-4 with ((d)Ipc)(2)BH and subsequent crotylboration of achiral aldehydes with the product crotylborane (S)-E-5 at -78 degrees C provide (E)-delta-silyl-anti-homoallylic alcohols 6 in 71-89% yield and with 93-96% ee. Intriguingly, mismatched double asymmetric crotylboration reactions of enantioenriched chiral aldehydes 20 with (S)-E-5 proceed under Curtin-Hammett control to give anti-beta-hydroxylcrotylsilanes 24 as the only products. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.098

文献信息

• Development of α,α-Disubstituted Crotylboronate Reagents and Stereoselective Crotylation via Brønsted or Lewis Acid Catalysis
  作者：Shang Gao、Meng Duan、Qianzhen Shao、K. N. Houk、Ming Chen

  DOI：10.1021/jacs.0c04107

  日期：2020.10.28

  Stereochemical models for BF3·OEt2-catalyzed reactions are proposed to rationalize the Z-selective allyl additions. These reactions generate highly valuable homoallylic alcohol products with a stereodefined trisubstituted alkene unit. The synthetic utility is further demonstrated by the total syntheses of salinipyrones A and B.

  报道了 α,α-二取代巴豆基硼酸酯试剂的开发。手性布朗斯台德酸催化不对称醛加成与开发的 E-巴豆基硼试剂产生 (E)-anti-1,2-oxaborinan-3-enes，具有优异的对映选择性和 E-选择性。在 BF3·OEt2 催化下，立体选择性被逆转，并且从相同的 E-巴豆基硼试剂中获得了具有优异 Z-选择性的 (Z)-δ-硼基-抗高烯丙醇。Z-巴豆基硼试剂还参与 ·OEt2催化的巴豆化反应以提供具有良好Z-选择性的(Z)-δ-硼基-syn-高烯丙醇。DFT 计算确定了观察到的手性布朗斯台德酸催化的不对称烯丙基化的对映选择性和立体选择性的起源。 ·OEt2 催化反应的立体化学模型被提出来合理化Z-选择性烯丙基加成。这些反应生成具有立体定义的三取代烯烃单元的高价值高烯丙醇产品。Salinipyrones A 和 B 的全合成进一步证明了合成效用。
• Reprint of: Enantiodivergent hydroboration reactions of a racemic allenylsilane with diisopinocampheylborane and Curtin–Hammett controlled double asymmetric crotylboration reactions of (S)-E-α-phenyldimethylsilyl(ddiisopinocampheyl)-crotylborane
  作者：Ming Chen、William R. Roush

  DOI：10.1016/j.tet.2013.06.053

  日期：2013.9

  The enantiodivergent hydroboration reactions of racemic allenylsilane (+/-)-4 with ((d)Ipc)(2)BH and subsequent crotylboration of achiral aldehydes with the product crotylborane (S)-E-5 at -78 degrees C provide (E)-delta-silyl-anti-homoallylic alcohols 6 in 71-89% yield and with 93-96% ee. Intriguingly, mismatched double asymmetric crotylboration reactions of enantioenriched chiral aldehydes 20 with (S)-E-5 proceed under Curtin-Hammett control to give anti-beta-hydroxylcrotylsilanes 24 as the only products. (C) 2013 Elsevier Ltd. All rights reserved.