N'-[1-((4S,5S)-4,5-Bis-isopropoxymethyl-[1,3]dioxolan-2-yl)-meth-(E)-ylidene]-N,N-dimethyl-hydrazine | 202280-34-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N'-[1-((4S,5S)-4,5-Bis-isopropoxymethyl-[1,3]dioxolan-2-yl)-meth-(E)-ylidene]-N,N-dimethyl-hydrazine
• CAS: 202280-34-0
• 化学式: C₁₄H₂₈N₂O₄
• 分子量: 288.387
• InChiKey: IPADDTQXXNXXCV-STQMWFEESA-N

反应信息

• 作为反应物：
  描述：

  N'-[1-((4S,5S)-4,5-Bis-isopropoxymethyl-[1,3]dioxolan-2-yl)-meth-(E)-ylidene]-N,N-dimethyl-hydrazine 在 Ranei Ni 作用下， 以 甲醇 、 甲苯 为溶剂， 生成 C-[(S)-C-((4S,5S)-4,5-Bis-isopropoxymethyl-[1,3]dioxolan-2-yl)-C-phenyl]-methylamine
  参考文献：
  名称：

  1,4-Di-O-tert-alkyl-l-threitols as Chiral Auxiliaries in the Asymmetric Nucleophilic Addition of Alkyllithiums to Hydrazones

  摘要：

  The applications of 1,4-di-O-tert-alkyl-L-threitols as chiral auxiliaries in the asymmetric nucleophilic addition of alkyllithiums to hydrazones are investigated. Chiral acetal-hydrazones 9, obtained from the chiral acetals 8 by ozonolysis followed by treatment with dimethylhydrazine, are allowed to react with organolithium reagents in toluene at -78 degrees C to give 15 with excellent diastereoselectivity. The stereochemical assignments were based an the X-ray crystal structure of 17a. The absolute configuration at C-2 Of the major isomer of the adducts 15 was thereby determined to be S. The nucleophile thus attacked from the si face of the C=N moiety. The effect of solvent on the diastereoselectivity of the reactions of 9 with organolithium reagents is reported. Polar aprotic solvent shows poor diastereoselectivity, and the diastereoselectivity; is reversed when the reaction is carried out in THF. Reaction of dl-14 with methyllithium has been studied for comparison purposes and the reaction shows the opposite selectivity. Chelation intermediates 18 and 26 are proposed for these reactions to account for the observed stereoselectivities.

  DOI：

  10.1021/jo971700y
• 作为产物：
  描述：

  (2S,3S)-1,4-Diisopropoxy-butane-2,3-diol 在 二甲基硫 、 4-甲基苯磺酸吡啶 、 臭氧 作用下， 以 苯 为溶剂， 生成 N'-[1-((4S,5S)-4,5-Bis-isopropoxymethyl-[1,3]dioxolan-2-yl)-meth-(E)-ylidene]-N,N-dimethyl-hydrazine
  参考文献：
  名称：

  1,4-Di-O-tert-alkyl-l-threitols as Chiral Auxiliaries in the Asymmetric Nucleophilic Addition of Alkyllithiums to Hydrazones

  摘要：

  The applications of 1,4-di-O-tert-alkyl-L-threitols as chiral auxiliaries in the asymmetric nucleophilic addition of alkyllithiums to hydrazones are investigated. Chiral acetal-hydrazones 9, obtained from the chiral acetals 8 by ozonolysis followed by treatment with dimethylhydrazine, are allowed to react with organolithium reagents in toluene at -78 degrees C to give 15 with excellent diastereoselectivity. The stereochemical assignments were based an the X-ray crystal structure of 17a. The absolute configuration at C-2 Of the major isomer of the adducts 15 was thereby determined to be S. The nucleophile thus attacked from the si face of the C=N moiety. The effect of solvent on the diastereoselectivity of the reactions of 9 with organolithium reagents is reported. Polar aprotic solvent shows poor diastereoselectivity, and the diastereoselectivity; is reversed when the reaction is carried out in THF. Reaction of dl-14 with methyllithium has been studied for comparison purposes and the reaction shows the opposite selectivity. Chelation intermediates 18 and 26 are proposed for these reactions to account for the observed stereoselectivities.

  DOI：

  10.1021/jo971700y