(2S,3S)-1,4-bis(diphenylamino)-2,3-O-isopropylidenebutane-2,3-diol

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2S,3S)-1,4-bis(diphenylamino)-2,3-O-isopropylidenebutane-2,3-diol
• 英文别名: (+)-(4S,5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane；(+)-(4s,5s)-2,2-Dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane；N-[[(4S,5S)-2,2-dimethyl-5-[(N-phenylanilino)methyl]-1,3-dioxolan-4-yl]methyl]-N-phenylaniline
• 化学式: C₃₁H₃₂N₂O₂
• 分子量: 464.607
• InChiKey: DCZCZLMHTGUGSH-KYJUHHDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  24.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  二苯胺 、 (-)-1,4-二-O-甲苯磺酰基-2,3-O-异亚丙基-L-苏糖醇 在 萘 、 sodium 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 24.5h， 以50%的产率得到(2S,3S)-1,4-bis(diphenylamino)-2,3-O-isopropylidenebutane-2,3-diol
  参考文献：
  名称：

  摘要：

  The reaction of sodium diphenylamide with 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane,gave (+)-(4S,5S)-2,2-dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane, which was brought into complex formation with cobalt chloride. Treatment of 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane with sodium N-methylanilide resulted in cleavage of the S-O bond in the p-toluenesulfonate moiety with formation of N-methyl-N-phenyl-p-toluenesulfonamide and 4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane disodium salt. Diethyl (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate reacted with methylamine to give the corresponding dicarboxamide which was reduced with lithium aluminum hydride to (4S,5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane having chiral carbon and nitrogen atoms.

  DOI：

  10.1023/a:1022528016140

文献信息

• Chiral 4-(Diphenylphosphanyl)-1-(dialkylamino)butane Ligands – Synthesis, Applications in Asymmetric Alkylation and Theoretical Study
  作者：Fabien Robert、Françoise Delbecq、Christelle Nguefack、Denis Sinou

  DOI：10.1002/(sici)1099-0682(200002)2000:2<351::aid-ejic351>3.0.co;2-q

  日期：2000.2

  3-O-isopropylidene-D-threitol. These ligands, associated with Pd2(dba)3, gave enantioselectivities of up to 75% in the alkylation of racemic 1,3-diphenylprop-2-enyl acetate with dimethyl malonate anion. A theoretical study shows the important role played by two factors in the alkylation reaction: steric control, leading to the formation of a unique diastereoisomer of the π-allylpalladium complex, and orbital control

  各种 4-(二苯基膦基)-1-(二烷基氨基) 丁烷配体由商业 (2S,3S)-2,3-O-异亚丙基-D-苏糖醇制备。这些与 Pd2(dba)3 相关的配体在外消旋 1,3-二苯基丙-2-烯基乙酸酯与丙二酸二甲酯阴离子的烷基化反应中具有高达 75% 的对映选择性。一项理论研究表明，两个因素在烷基化反应中起着重要作用：空间控制，导致形成独特的 π-烯丙基钯配合物的非对映异构体，以及轨道控制，将亲核试剂的攻击定向到磷原子.
• ——
  作者：B. A. Shainyan、L. O. Nindakova、M. V. Ustinov、N. N. Chipanina、L. V. Sherstyannikova

  DOI：10.1023/a:1022528016140

  日期：——

  The reaction of sodium diphenylamide with 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane,gave (+)-(4S,5S)-2,2-dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane, which was brought into complex formation with cobalt chloride. Treatment of 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane with sodium N-methylanilide resulted in cleavage of the S-O bond in the p-toluenesulfonate moiety with formation of N-methyl-N-phenyl-p-toluenesulfonamide and 4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane disodium salt. Diethyl (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate reacted with methylamine to give the corresponding dicarboxamide which was reduced with lithium aluminum hydride to (4S,5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane having chiral carbon and nitrogen atoms.