(2S,3S)-1,4-Di-tert-butoxy-butane-2,3-diol | 166248-38-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S)-1,4-Di-tert-butoxy-butane-2,3-diol
• 英文别名: (2S,3S)-1,4-bis[(2-methylpropan-2-yl)oxy]butane-2,3-diol
• CAS: 166248-38-0
• 化学式: C₁₂H₂₆O₄
• 分子量: 234.336
• InChiKey: VEBWBPPTOZLJIN-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3S)-1,4-Di-tert-butoxy-butane-2,3-diol 在 二甲基硫 、 4-甲基苯磺酸吡啶 、 臭氧 作用下， 以 甲苯 、 苯 为溶剂， 生成 N'-[(R)-((4S,5S)-4,5-Bis-tert-butoxymethyl-[1,3]dioxolan-2-yl)-phenyl-methyl]-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
• 作为产物：
  描述：

  甲基碘化镁 、 1.2;3.4-Di-O-isopropyliden-D-threit 以 乙醚 、 苯 为溶剂， 反应 20.0h， 以80%的产率得到(2S,3S)-1,4-Di-tert-butoxy-butane-2,3-diol
  参考文献：
  名称：

  Highly Diastereoselective Ring-Opening Reactions of Chiral Acetals with Secondary or Sterically Hindered Grignard Reagents

  摘要：

  There has been an increasing interest in the stereoselective ring opening of acetals by means of nucleophiles.(1-4) Most of these approaches involve the preferential complex formation of acetals with a Lewis acid and subsequent invertive substitution by nucleophiles (Scheme 1).(2) The retentive ring cleavage of acetals has been investigated only briefly, mostly related to the reductive ring opening with metal hydrides.(3,4) Recently, Yamamoto and his co-workers reported the highly diastereoselective retentive alkylation of chiral acetals using novel organoaluminum reagents.(4) However, only methyl- or primary alkylaluminum reagents can be used. We now wish to describe our investigations on the highly diastereoselective reactions of secondary or sterically bulky Grignard reagents with chiral acetals prepared from aldehydes and tunable chiral diols.

  DOI：

  10.1021/jo00105a041

文献信息

• Diastereoselective Simmons−Smith Cyclopropanation of α,β-Unsaturated Cycloalkenones Using Tunable Diol as Chiral Auxiliary
  作者：Sue-Min Yeh、Li-Hsing Huang、Tien-Yau Luh

  DOI：10.1021/jo960181g

  日期：1996.1.1
• Chiral Bisazafulleroids
  作者：Clifton K.-F. Shen、Kuo-Ming Chien、Chiun-Gung Juo、Guor-Rong Her、Tien-Yau Luh

  DOI：10.1021/jo961804t

  日期：1996.1.1

  The reactions of C-60 with C-2 chiral 1,4-tert-alkoxy-2,3-bisazidobutanes give the corresponding chiral bisazafulleroids 2. The enantiomeric pairs of chiral bisazafulleroids 2 exhibit mirror image CD curves.
• 1,4-Di-<i>O-tert-</i>alkyl-<scp>l</scp>-threitols as Chiral Auxiliaries in the Asymmetric Nucleophilic Addition of Alkyllithiums to Hydrazones
  作者：Yu-Tsai Hsieh、Gene-Hsiang Lee、Yu Wang、Tien-Yau Luh

  DOI：10.1021/jo971700y

  日期：1998.3.1

  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.
• Highly Diastereoselective Ring-Opening Reactions of Chiral Acetals with Secondary or Sterically Hindered Grignard Reagents
  作者：Tien-Min Yuan、Sue-Min Yeh、Yu-Tsai Hsieh、Tien-Yau Luh

  DOI：10.1021/jo00105a041

  日期：1994.12

  There has been an increasing interest in the stereoselective ring opening of acetals by means of nucleophiles.(1-4) Most of these approaches involve the preferential complex formation of acetals with a Lewis acid and subsequent invertive substitution by nucleophiles (Scheme 1).(2) The retentive ring cleavage of acetals has been investigated only briefly, mostly related to the reductive ring opening with metal hydrides.(3,4) Recently, Yamamoto and his co-workers reported the highly diastereoselective retentive alkylation of chiral acetals using novel organoaluminum reagents.(4) However, only methyl- or primary alkylaluminum reagents can be used. We now wish to describe our investigations on the highly diastereoselective reactions of secondary or sterically bulky Grignard reagents with chiral acetals prepared from aldehydes and tunable chiral diols.