2-(<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>heptan-1-yl>methylthio)nicotinic acid | 202257-36-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-(<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>heptan-1-yl>methylthio)nicotinic acid
• 英文别名: 2-[[(1S,2R,4R)-2-hydroxy-7,7-dimethyl-1-bicyclo[2.2.1]heptanyl]methylsulfanyl]pyridine-3-carboxylic acid
• CAS: 202257-36-1
• 化学式: C₁₆H₂₁NO₃S
• 分子量: 307.414
• InChiKey: ZDIRMTSNFYJNQE-NSODJVPESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  95.7
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>heptan-1-yl>methylthio)nicotinic acid 在 sodium hydroxide 、 次氯酸叔丁酯 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (R_S)-2-(<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>heptan-1-yl>methanesulfinyl)nicotinic acid
  参考文献：
  名称：

  Stereochemical Research on the Hydrolysis of Optically Pure Spirosulfuranes:  Efficient Synthesis of Chiral Sulfoxides with Completely Opposite Stereochemistry

  摘要：

  The synthesis of optically pure alkoxy(acyloxy)spirosulfuranes 5a-e, using the 2-exo-hydroxy-10-bornyl group as a chiral ligand, has been developed in high yield and with excellent diastereoselectivity. The X-ray analyses of 5a and 5b indicated that the spirosulfuranes have the trigonal bipyramidal (TBP) structures around the sulfur atom. Recrystallization of 5c,d from moist solvent (95% EtOH aq) gave sulfoxides 7c,d, respectively, as single products with an S-s absolute configuration at the sulfur atom. In contrast, hydrolysis of sulfuranes 5b,c,d under the basic conditions afforded the sulfoxides 8b,c,d, with an R-s absolute configuration at the sulfur atom, in high yield and with excellent diastereoselectivity. The stereochemical and mechanistic study of the hydrolysis of spirosulfuranes was performed by using spirosulfurane 5a. Hydrolysis of 5a under acidic and basic conditions gave, diastereoselectively, the corresponding sulfoxides 7a and 8a with the opposite absolute configuration at the sulfur atom. The structures of the sulfoxides 7a,c and 8a,b were confirmed by X-ray crystallographic analyses. The mass spectral and O-17 NMR studies of the sulfoxides 7a-(18(17))O and 8a-(18(17))O, which were prepared by the hydrolysis of 5a with isotopically labeled water, revealed definitely that the oxygen atom bound to the sulfur atom in these compounds derives from water. The possible mechanisms of the reactions which account for the observed stereochemical results have been suggested.

  DOI：

  10.1021/jo981330t
• 作为产物：
  描述：

  2-巯基烟酸 、 (1S)-(-)-10-iodo-2-exobornanol 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 5.5h， 以52%的产率得到2-(<(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo<2.2.1>heptan-1-yl>methylthio)nicotinic acid
  参考文献：
  名称：

  Stereochemical Research on the Hydrolysis of Optically Pure Spirosulfuranes:  Efficient Synthesis of Chiral Sulfoxides with Completely Opposite Stereochemistry

  摘要：

  The synthesis of optically pure alkoxy(acyloxy)spirosulfuranes 5a-e, using the 2-exo-hydroxy-10-bornyl group as a chiral ligand, has been developed in high yield and with excellent diastereoselectivity. The X-ray analyses of 5a and 5b indicated that the spirosulfuranes have the trigonal bipyramidal (TBP) structures around the sulfur atom. Recrystallization of 5c,d from moist solvent (95% EtOH aq) gave sulfoxides 7c,d, respectively, as single products with an S-s absolute configuration at the sulfur atom. In contrast, hydrolysis of sulfuranes 5b,c,d under the basic conditions afforded the sulfoxides 8b,c,d, with an R-s absolute configuration at the sulfur atom, in high yield and with excellent diastereoselectivity. The stereochemical and mechanistic study of the hydrolysis of spirosulfuranes was performed by using spirosulfurane 5a. Hydrolysis of 5a under acidic and basic conditions gave, diastereoselectively, the corresponding sulfoxides 7a and 8a with the opposite absolute configuration at the sulfur atom. The structures of the sulfoxides 7a,c and 8a,b were confirmed by X-ray crystallographic analyses. The mass spectral and O-17 NMR studies of the sulfoxides 7a-(18(17))O and 8a-(18(17))O, which were prepared by the hydrolysis of 5a with isotopically labeled water, revealed definitely that the oxygen atom bound to the sulfur atom in these compounds derives from water. The possible mechanisms of the reactions which account for the observed stereochemical results have been suggested.

  DOI：

  10.1021/jo981330t

文献信息

• Acidic and Basic Hydrolysis of an Optically Pure Spiro-λ⁴-sulfurane:  Completely Opposite Stereochemical Outcome
  作者：Jian Zhang、Shinichi Saito、Toru Koizumi

  DOI：10.1021/ja973039l

  日期：1998.2.1