RS-l-menthyl 3,5-di-tert-butyl-4-methoxybenzenesulfinate | 227078-68-4

• 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: RS-l-menthyl 3,5-di-tert-butyl-4-methoxybenzenesulfinate
• 英文别名: R_S-l-menthyl 3,5-di-tert-butyl-4-methoxybenzenesulfinate；(-)-menthyl-(S)-3,5-di-tert-butyl-4-methoxybenzenesulfinate
• CAS: 227078-68-4
• 化学式: C₂₅H₄₂O₃S
• 分子量: 422.673
• InChiKey: WYXHHFJGANJNRO-HIXRATTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.79
• 重原子数：
  29.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 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：

  甲基碘化镁 、 RS-l-menthyl 3,5-di-tert-butyl-4-methoxybenzenesulfinate 以 四氢呋喃 、 乙醚 为溶剂， 以93%的产率得到(S)-(-)-3,5-di-tert-butyl-4-methoxyphenyl methyl sulfoxide
  参考文献：
  名称：

  Highly Diastereoselective Intermolecular β-Addition of Alkyl Radicals to Chiral 2-(Arylsulfinyl)-2-cycloalkenones

  摘要：

  The diastereoselectivity of intermolecular beta-addition of alkyl radicals to 2-(arylsulfinyl)-acycloalkenones depends largely upon the structure of the arylsulfinyl group. The reaction of a-cyclopentenones or 2-cyclohexenones having a sterically bulky arylsulfinyl group such as (3,5-di-tert-butyl-4-methoxyphenyl)-sulfinyl, (2,4,6-triisopropylphenyl)sulfinyl or (2,4,6-trimethylphenyl)-sulfinyl group gives 3-alkyl-2-(arylsulfinyl)-1-cyclopentanones or 3-alkyl-2-(arylsulfinyl)-1-cyclohexanones in excellent yields and with high diastereoselectivity. Both the X-ray crystallographic analysis and the NOE experiment in the H-1 NMR spectrum of (S)-2-[(2,4,6-triisopropylphenyl)-sulfinyl]- and (S)-2-[(2,4,6-trimethylphenyl)sulfinyl]-2-cyclopentenone reveal an effective shielding of one of the olefin faces at the beta-position by o-isopropyl and o-methyl groups. The addition of bidentate Lewis acids reverses the stereoselection through chelating the intermediates to give the addition products with high diastereoselectivity.

  DOI：

  10.1021/jo971093e
• 作为产物：
  描述：

  3,5-bis(1,1-dimethylethyl)-4-methoxybenzenesulfonic acid 在 SOSl₂ 、 三乙胺 、 三甲氧基磷 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.5h， 生成 RS-l-menthyl 3,5-di-tert-butyl-4-methoxybenzenesulfinate
  参考文献：
  名称：

  Highly Diastereoselective Intermolecular β-Addition of Alkyl Radicals to Chiral 2-(Arylsulfinyl)-2-cycloalkenones

  摘要：

  The diastereoselectivity of intermolecular beta-addition of alkyl radicals to 2-(arylsulfinyl)-acycloalkenones depends largely upon the structure of the arylsulfinyl group. The reaction of a-cyclopentenones or 2-cyclohexenones having a sterically bulky arylsulfinyl group such as (3,5-di-tert-butyl-4-methoxyphenyl)-sulfinyl, (2,4,6-triisopropylphenyl)sulfinyl or (2,4,6-trimethylphenyl)-sulfinyl group gives 3-alkyl-2-(arylsulfinyl)-1-cyclopentanones or 3-alkyl-2-(arylsulfinyl)-1-cyclohexanones in excellent yields and with high diastereoselectivity. Both the X-ray crystallographic analysis and the NOE experiment in the H-1 NMR spectrum of (S)-2-[(2,4,6-triisopropylphenyl)-sulfinyl]- and (S)-2-[(2,4,6-trimethylphenyl)sulfinyl]-2-cyclopentenone reveal an effective shielding of one of the olefin faces at the beta-position by o-isopropyl and o-methyl groups. The addition of bidentate Lewis acids reverses the stereoselection through chelating the intermediates to give the addition products with high diastereoselectivity.

  DOI：

  10.1021/jo971093e

文献信息

• Chiral Heterodisulfoxide Ligands in Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to Chromenones
  作者：Fuzhong Han、Guihua Chen、Xiangyang Zhang、Jian Liao

  DOI：10.1002/ejoc.201100387

  日期：2011.6

  A new family of benzene-based chiral heterodisulfoxide ligands L1-L5 was synthesized in a single step. These disulfoxide ligands were applied in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to chromenones. The addition of diverse arylboronic acids to chromenones proceeds smoothly in up to 70% yield with up to 95% ee.

  一个新的苯基手性杂二亚砜配体 L1-L5 是一步合成的。这些二亚砜配体用于铑催化的芳基硼酸与色酮的不对称 1,4-加成反应。将各种芳基硼酸添加到色酮中的过程可以顺利进行，产率高达 70%，ee 高达 95%。
• An improved and efficient procedure for the preparation of chiral sulfinates from sulfonyl chloride using triphenylphosphine
  作者：Yoshihiko Watanabe、Nobuyuki Mase、Moto-aki Tateyama、Takeshi Toru

  DOI：10.1016/s0957-4166(99)00066-x

  日期：1999.2

  An improved procedure of the Sharpless method for the preparation of chiral sulfinates by triphenylphosphine is described. A mixture of sulfonyl chlorides and diacetone-d-glucose or l-menthol in the presence of triethylamine was treated with triphenylphosphine in CH2Cl2 at 0°C to give the sulfinates in good yields.

  描述了通过三苯基膦制备手性亚磺酸盐的Sharpless方法的改进方法。在三乙胺存在下，将磺酰氯和双丙酮-d-葡萄糖或1-薄荷醇的混合物在0℃下在CH 2 Cl 2中用三苯基膦处理，以良好的产率得到亚磺酸盐。