(1r,3r,5r,7r)-2-(propa-1,2-dien-1-yloxy)adamantine | 1292246-27-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1r,3r,5r,7r)-2-(propa-1,2-dien-1-yloxy)adamantine
• 英文别名: (3s,5s,7s)-1-(propa-1,2-dien-1-yloxy)adamantane
• CAS: 1292246-27-5
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: ROVXEPBTKUPSRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  甲基 6-O-[二甲基(2-甲基-2-丙基)硅烷基]-alpha-D-吡喃甘露糖苷 、 (1r,3r,5r,7r)-2-(propa-1,2-dien-1-yloxy)adamantine 在 palladium diacetate 、 N,N-二异丙基乙胺 、 (1R,2R)-(+)-1,2-二氨基环己烷-N,N′-双(2-苯基膦-1-萘酰基) 、 10H-二苯并[B,E][1,4]氧杂硼杂环己烷-10-醇 作用下， 以 甲苯 为溶剂， 以83 %的产率得到(2R,3R,4S,5S,6S)-4-(((S)-1-(((3R,5R,7R)-adamantan-1-yl)oxy)allyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-6-methoxytetrahydro-2H-pyran-3,5-diol
  参考文献：
  名称：

  Asymmetric Pd/Organoboron‐Catalyzed Site‐Selective Carbohydrate Functionalization with Alkoxyallenes Involving Noncovalent Stereocontrol

  摘要：

  Herein, we demonstrate the robustness of a synergistic chiral Pd/organoboron system in tackling a challenging suite of site‐, regio‐, enantio‐ and diastereoselectivity issues across a considerable palette of biologically relevant carbohydrate polyols, when prochiral alkoxyallenes were employed as electrophiles. In view of the burgeoning role of noncovalent interactions (NCIs) in stereoselective carbohydrate synthesis, our mechanistic experiments and DFT modeling of the reaction path unexpectedly revealed that NCIs such as hydrogen bonding and CH‐π interactions between the resting states of the Pd‐π‐allyl complex and the borinate saccharide are critically involved in the stereoselectivity control. Our strategy thus illuminates the untapped potential of harnessing NCIs in the context of transition metal catalysis to tackle stereoselectivity challenges in carbohydrate functionalization.

  DOI：

  10.1002/anie.202400912
• 作为产物：
  描述：

  1-adamantyl propargyl ether 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 (1r,3r,5r,7r)-2-(propa-1,2-dien-1-yloxy)adamantine
  参考文献：
  名称：

  Asymmetric Pd/Organoboron‐Catalyzed Site‐Selective Carbohydrate Functionalization with Alkoxyallenes Involving Noncovalent Stereocontrol

  摘要：

  Herein, we demonstrate the robustness of a synergistic chiral Pd/organoboron system in tackling a challenging suite of site‐, regio‐, enantio‐ and diastereoselectivity issues across a considerable palette of biologically relevant carbohydrate polyols, when prochiral alkoxyallenes were employed as electrophiles. In view of the burgeoning role of noncovalent interactions (NCIs) in stereoselective carbohydrate synthesis, our mechanistic experiments and DFT modeling of the reaction path unexpectedly revealed that NCIs such as hydrogen bonding and CH‐π interactions between the resting states of the Pd‐π‐allyl complex and the borinate saccharide are critically involved in the stereoselectivity control. Our strategy thus illuminates the untapped potential of harnessing NCIs in the context of transition metal catalysis to tackle stereoselectivity challenges in carbohydrate functionalization.

  DOI：

  10.1002/anie.202400912

文献信息

• Cationic Gold(I)-Catalyzed Intermolecular [4+2] Cycloaddition between Dienes and Allenyl Ethers
  作者：Guan Wang、Yue Zou、Zhiming Li、Quanrui Wang、Andreas Goeke

  DOI：10.1002/adsc.201000597

  日期：2011.3.7

  Simple allenyl ethers have been shown to be efficiently activated by cationic gold(I) catalysts to form reactive dienophiles in intermolecular Diels–Alder reactions. A range of different dienes give the cycloaddition products in moderate to excellent yields and good selectivity.

  简单的烯基醚已被阳离子金（I）催化剂有效活化，在分子间Diels-Alder反应中形成反应性亲二烯体。一系列不同的二烯使环加成产物的产率中等至优异，并且具有良好的选择性。
• Diastereodivergent Synthesis of β‐Amino Alcohols by Dual‐Metal‐Catalyzed Coupling of Alkoxyallenes with Aldimine Esters
  作者：Minghui Zhu、Qinglong Zhang、Weiwei Zi

  DOI：10.1002/anie.202014510

  日期：2021.3.15

  method for stereoselective access to complementary diastereomers would be highly desirable. Herein, we report a method for dual‐metal‐catalyzed diastereodivergent coupling of alkoxyallenes with aldimine esters. By carefully selecting the two metals and appropriate chiral ligands, we could synthesize both syn‐ and anti‐β‐amino alcohol motifs with high enantioselectivity and diastereoselectivity from the same

  两个顺式-和反-β -氨基醇是在天然产物，药物分子，手性配体和催化剂共同的结构基序。但是，合成这些基序的当前可用方法仅限于仅产生一种非对映异构体。因此，非常需要开发一种立体方法，以选择性地互补互补非对映异构体。本文中，我们报告了烷氧基丙二烯与醛亚胺酯的双金属催化非对映异构偶联方法。通过仔细选择两种金属和合适的手性配体，我们可以合成顺式和反式来自同一套起始材料的具有高对映选择性和非对映选择性的β-氨基醇基序。此外，可以实现β-氨基醇的所有四种立体异构体的立体发散性合成。我们通过简洁地合成两种β-氨基醇天然产物Mycestericins F和G证明了该方法的合成效用。