(R)-N-(2,3-dihydroxyprop-1-yl)-9-fluorenimine

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (R)-N-(2,3-dihydroxyprop-1-yl)-9-fluorenimine
• 英文别名: (2R)-3-(fluoren-9-ylideneamino)propane-1,2-diol
• 化学式: C₁₆H₁₅NO₂
• 分子量: 253.301
• InChiKey: YJCISMJSBRGJMD-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  52.8
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  9-芴酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 potassium osmate(VI) 、 (DHQD)2PYDZ 、 四氯化钛 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 甲苯 、 叔丁醇 为溶剂， 反应 2.0h， 生成 (R)-N-(2,3-dihydroxyprop-1-yl)-9-fluorenimine
  参考文献：
  名称：

  The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.

  摘要：

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.

  DOI：

  10.1021/ja00149a003

文献信息

• The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.
  作者：E. J. Corey、Angel Guzman-Perez、Mark C. Noe

  DOI：10.1021/ja00149a003

  日期：1995.11

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.