2-((R)-1-Phenyl-prop-2-ynyloxy)-tetrahydro-pyran | 708277-98-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 2-((R)-1-Phenyl-prop-2-ynyloxy)-tetrahydro-pyran
• CAS: 708277-98-9
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: JWDVGHWVCACZHY-LSLKUGRBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-((R)-1-Phenyl-prop-2-ynyloxy)-tetrahydro-pyran 在 正丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 15.0h， 生成 (R)-1-phenyl-3-dimethyl(ethyl)silyl-2-propyn-1-ol
  参考文献：
  名称：

  Rhodium-Catalyzed Asymmetric Synthesis of Indanones:  Development of a New “Axially Chiral” Bisphosphine Ligand

  摘要：

  A rhodium-catalyzed asymmetric isomerization of racemic alpha-arylpropargyl alcohols to beta-chiral indanones has been developed. High enantioselectivity has been realized by the use of a newly developed axially chiral bisphosphine ligand. This ligand is unique in the sense that its axial chirality is fixed to a single configuration upon complexation to a transition metal due to other chiral axes existing within the same molecule.

  DOI：

  10.1021/ja056584s
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 (S)-1-苯基-2-丙炔-1-醇 在 盐酸 作用下， 反应 2.0h， 生成 2-((R)-1-Phenyl-prop-2-ynyloxy)-tetrahydro-pyran
  参考文献：
  名称：

  Rhodium-Catalyzed Asymmetric Synthesis of Indanones:  Development of a New “Axially Chiral” Bisphosphine Ligand

  摘要：

  A rhodium-catalyzed asymmetric isomerization of racemic alpha-arylpropargyl alcohols to beta-chiral indanones has been developed. High enantioselectivity has been realized by the use of a newly developed axially chiral bisphosphine ligand. This ligand is unique in the sense that its axial chirality is fixed to a single configuration upon complexation to a transition metal due to other chiral axes existing within the same molecule.

  DOI：

  10.1021/ja056584s

文献信息

• Mild and efficient palladium(<scp>ii</scp>)-catalyzed racemization of allenes
  作者：Attila Horváth、Jan-E. Bäckvall

  DOI：10.1039/b316482a

  日期：——

  Allenes undergo racemization in the presence of catalytic amounts of Pd(OAc)2/LiBr under mild conditions; the reaction proceeds via a bromopalladation–debromopalladation sequence and tolerates various functional groups.

  在温和条件下，烯丙基体系在催化量的Pd(OAc)2/LiBr存在下发生外消旋化；反应通过溴钯化-去溴钯化序列进行，并且对各种官能团具有耐受性。
• Preparation of Optically Pure Propargylic and Allylic Alcohols from 2-(Trimethylsilyl)vinyl Sulfoxides as a Chiral Ethynyl Anion Synthon:  Computational Studies on Elimination Reaction of 2-(Trimethylsilyl)vinyl Sulfoxides
  作者：Shuichi Nakamura、Shinya Kusuda、Kiyoshi Kawamura、Takeshi Toru

  DOI：10.1021/jo0157223

  日期：2002.2.1

  The reaction of the alpha-carbanion derived from (trimethylsilyl)vinyl sulfoxides with aldehydes afforded a diastereomeric mixture of the products. Each diastereomer was subjected to specific elimination reactions to give optically pure propargylic, trimethylsilylated propargylic, and allylic alcohols. Acceleration of the sulfenic acid-elimination from the beta-silylvinyl sulfoxide was demonstrated

  衍生自（三甲基甲硅烷基）乙烯基亚砜的α-碳负离子与醛的反应提供了产物的非对映异构体混合物。使每种非对映异构体进行特定的消除反应，得到光学纯的炔丙醇，三甲基甲硅烷基化的炔丙醇和烯丙基醇。从头算起证明从β-甲硅烷基乙烯基亚砜中消除亚硫酸的加速主要归因于甲硅烷基的β-作用。