(Z)-(1R,4'R)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-but-2-ene-1-ol | 154842-35-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-(1R,4'R)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-but-2-ene-1-ol
• 英文别名: (Z)-(1R,4'R)-1-(2,2-dimethyl-1,3-dioxolane-4-yl)but-2-en-1-ol；(2R,3R)-1,2-O-isopropylidene-(4Z)-hexene-1,2,3-triol；(Z,1R)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]but-2-en-1-ol
• CAS: 154842-35-0
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: KXFGFBMUQMLNGZ-ILFIBXKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-(1R,4'R)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-but-2-ene-1-ol 在 sodium tetrahydroborate 、 sodium hydride 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 3-O-benzyl-1,2-O-isopropylidene-D-threitol
  参考文献：
  名称：

  Diastereoselective addition of lower order vinylcuprates to (R)-2,3-O-Isopropylideneglyceraldehyde

  摘要：

  Highly syn or anti selective addition of lower order lithium vinylcuprates generated from alkenyl bromides 1 to (R)-2,3-O-isopropylideneglyceraldehyde (2) can be achieved, respectively, depending on the substitution pattern of the vinyl moiety and the solvent. Alpha-Trimethylsilyl substituted vinylcuprates possessing an alkyl substituent Z to copper react with excellent syn selectivity in ether whereas a highly anti selective addition is observed for cuprates bearing a hydrogen atom Z or alpha to the metal in THF. A model is proposed to rationalize these complementary selectivities.

  DOI：

  10.1016/s0040-4020(01)81551-9
• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 Pd-BaSO₄ 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 22.0~25.0 ℃ 、100.0 kPa 条件下， 生成 (Z)-(1R,4'R)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-but-2-ene-1-ol
  参考文献：
  名称：

  Synthesis of Optically Active β,γ-Unsaturated α-Amino Acids and of α,β-Unsaturated γ-Amino Acids. SN2- vs. SN2’-Dichotomy of the Mitsunobu Amination of Allylic Alcohols

  摘要：

  本文描述了从（R）-异丙叉甘油醛和乙基（S）-乳酸分别合成光学纯的β,γ-不饱和α-氨基酸和α,β-不饱和γ-氨基酸的新颖且高效的方法（总步骤为6-9步，总收率为10-30%）。关键步骤是手性仲烯丙醇与酞酰亚胺作为亲核试剂的 Mitsunobu 反应，首次观察到α,γ 烯丙基重排现象。研究了结构-α,γ 比例关系以及烯丙基重排的立体化学。α-取代过程通过干净的 SN2 反转进行，而γ-取代对应于亲核试剂的（E）-反向攻击，具有不同的立体选择性。

  DOI：

  10.1055/s-1995-3847

文献信息

• Stereoselective [2,3]-sigmatropic wittig rearrangement of benzyl ethers derived from vinylcuprate adducts of (R)-2,3-O-isopropylidenegiyceraldehyde
  作者：Peter Metz、Andreas Schoop

  DOI：10.1016/0040-4020(95)00497-v

  日期：1995.8

  (R)-2,3-O-isopropylideneglyceraldehyde (1) are converted to 3,4,5-trimethoxybenzyl ethers 3 by a one-pot desilylation/alkylation. After deprotonation using potassium t-butoxide/t-butyllithium/N, N N′ N′-tetramethylethylenediamine in t-butyl methyl ether at −78 °C, substrates 3 undergo a [2,3]-sigmatropic Wittig rearrangement with complete 1,3-chirality transfer and good simple diastereoselectivity to give

  通过一锅脱甲硅烷基化/烷基化将乙烯基铜碳酸锂加到（R）-2，3- O-异亚丙基甘油醛（1）中制备的烯丙醇2转化为3,4,5-三甲氧基苄基醚3。在-78°C下使用叔丁醇钾/叔丁基锂/ N，NN'N'-四甲基乙二胺在叔丁基甲基醚中进行质子化后，底物3发生[2,3]-σWittig重排，具有完整的1,3 -手性转移和良好的简单非对映选择性，以得到均烯丙基醇5为主要产物。
• Synthesis of Optically Active β,γ-Unsaturated α-Amino Acids and of α,β-Unsaturated γ-Amino Acids. SN2- vs. SN2’-Dichotomy of the Mitsunobu Amination of Allylic Alcohols
  作者：Johann Mulzer、Günther Funk

  DOI：10.1055/s-1995-3847

  日期：1995.1

  Novel and efficient syntheses (6-9 steps, overall yields 10-30%) are described for optically pure β,γ-unsaturated α-amino acids and α,β-unsaturated γ-amino acids, starting from (R)-isopropylidene glyceraldehyde and ethyl (S)-lactate, respectively. The key step is the Mitsunobu reaction of chiral secondary allylic alcohols with phthalimide as the nucleophile, where α,γ allylic transpositions are observed for the first time. The structure-α,γ-ratio-relationship is studied and also the stereochemistry of the allylic transposition. The α-substitution proceeds via clean SN2 inversion, whereas the γ-substitution corresponds to an (E)-anti attack of the nucleophilic with varying stereoselectivities.

  本文描述了从（R）-异丙叉甘油醛和乙基（S）-乳酸分别合成光学纯的β,γ-不饱和α-氨基酸和α,β-不饱和γ-氨基酸的新颖且高效的方法（总步骤为6-9步，总收率为10-30%）。关键步骤是手性仲烯丙醇与酞酰亚胺作为亲核试剂的 Mitsunobu 反应，首次观察到α,γ 烯丙基重排现象。研究了结构-α,γ 比例关系以及烯丙基重排的立体化学。α-取代过程通过干净的 SN2 反转进行，而γ-取代对应于亲核试剂的（E）-反向攻击，具有不同的立体选择性。
• Diastereoselective addition of lower order vinylcuprates to (R)-2,3-O-Isopropylideneglyceraldehyde
  作者：Peter Metz、Andreas Schoop

  DOI：10.1016/s0040-4020(01)81551-9

  日期：1993.1

  Highly syn or anti selective addition of lower order lithium vinylcuprates generated from alkenyl bromides 1 to (R)-2,3-O-isopropylideneglyceraldehyde (2) can be achieved, respectively, depending on the substitution pattern of the vinyl moiety and the solvent. Alpha-Trimethylsilyl substituted vinylcuprates possessing an alkyl substituent Z to copper react with excellent syn selectivity in ether whereas a highly anti selective addition is observed for cuprates bearing a hydrogen atom Z or alpha to the metal in THF. A model is proposed to rationalize these complementary selectivities.