(-)-(3S,4S,5S)-1-benzyloxycarbonyl-2-(tert-butoxycarbonyl)-5-tert-butyldimethylsilyloxymethyl-4-phenyl-3-vinylpyrazolidine | 224572-20-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 三唑并二氮卓类
• 英文名称: (-)-(3S,4S,5S)-1-benzyloxycarbonyl-2-(tert-butoxycarbonyl)-5-tert-butyldimethylsilyloxymethyl-4-phenyl-3-vinylpyrazolidine
• CAS: 224572-20-7
• 化学式: C₃₁H₄₄N₂O₅Si
• 分子量: 552.786
• InChiKey: SCLHXVBKDUWACC-VJGNERBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  39.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  68.31
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (-)-(3S,4S,5S)-1-benzyloxycarbonyl-2-(tert-butoxycarbonyl)-5-tert-butyldimethylsilyloxymethyl-4-phenyl-3-vinylpyrazolidine 在 jones reagent 作用下， 以95%的产率得到(+)-<(3S,4S,5S)-2-benzyloxycarbonyl-1-(tert-butoxycarbonyl)-4-phenyl-5-vinylpyrazolidine>carboxylic acid
  参考文献：
  名称：

  First Highly Regio- and Diastereoselective [3+2] Cycloaddition of Chiral Nonracemic Alkenyl Fischer Carbene Complexes with Diazomethane Derivatives: Preparation and Synthetic Applications of Enantiomerically Pure Δ2-Pyrazolines

  摘要：

  The [3+2] cycloaddition of alkenyl Fischer carbene complexes 1 and 6 with diazomethane derivatives to give Delta(2)-pyrazoline carbenes 2, 4, and 7 is described. The conversion of (-)-8-phenylmenthol-derived carbenes 6 into pyrazoline esters 9 through a one-pot cycloaddition-protection-oxidation is presented as an expeditious route to enantiomerically pure 3-alkoxycarbon-yl-Delta(2)-pyrazolines in good yields and in a highly regio- and diastereoselective manner. Pyrazolidines 13 were synthesized in excellent overall yields from 9 through pyrazolines 11 and 12, the diastereoselective reduction of C=N bond being the key step. Azaprolines 16 and 17 were prepared in very good yields from epimeric trans-13 or cis-13 by oxidative deprotection of the silylated hydroxy group. In an alternative reaction, the pyrazolidine ring of 13 was reduced to obtain protected open-chain 2,4-diamino alcohols 19 with three chiral centers.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<883::aid-chem883>3.0.co;2-0
• 作为产物：
  描述：

  (-)-(1R,2S,5R)-8-phenylmenthyl 3-((4S,5R)-1-tert-butoxycarbonyl-4,5-dihydro-4-phenyl-5-vinyl-1H-pyrazole)carboxylate 在 咪唑 、 sodium tetrahydroborate 、 三乙基硼氢化锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 33.0h， 生成 (-)-(3S,4S,5S)-1-benzyloxycarbonyl-2-(tert-butoxycarbonyl)-5-tert-butyldimethylsilyloxymethyl-4-phenyl-3-vinylpyrazolidine
  参考文献：
  名称：

  First Highly Regio- and Diastereoselective [3+2] Cycloaddition of Chiral Nonracemic Alkenyl Fischer Carbene Complexes with Diazomethane Derivatives: Preparation and Synthetic Applications of Enantiomerically Pure Δ2-Pyrazolines

  摘要：

  The [3+2] cycloaddition of alkenyl Fischer carbene complexes 1 and 6 with diazomethane derivatives to give Delta(2)-pyrazoline carbenes 2, 4, and 7 is described. The conversion of (-)-8-phenylmenthol-derived carbenes 6 into pyrazoline esters 9 through a one-pot cycloaddition-protection-oxidation is presented as an expeditious route to enantiomerically pure 3-alkoxycarbon-yl-Delta(2)-pyrazolines in good yields and in a highly regio- and diastereoselective manner. Pyrazolidines 13 were synthesized in excellent overall yields from 9 through pyrazolines 11 and 12, the diastereoselective reduction of C=N bond being the key step. Azaprolines 16 and 17 were prepared in very good yields from epimeric trans-13 or cis-13 by oxidative deprotection of the silylated hydroxy group. In an alternative reaction, the pyrazolidine ring of 13 was reduced to obtain protected open-chain 2,4-diamino alcohols 19 with three chiral centers.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<883::aid-chem883>3.0.co;2-0