(-)-(1R,2S,5R)-8-phenylmenthyl 3-((4R,5S)-1-tert-butoxycarbonyl-4,5-dihydro-4-phenyl-5-trimethylsilyl-1H-pyrazole)carboxylate | 196314-29-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (-)-(1R,2S,5R)-8-phenylmenthyl 3-((4R,5S)-1-tert-butoxycarbonyl-4,5-dihydro-4-phenyl-5-trimethylsilyl-1H-pyrazole)carboxylate
• 英文别名: 2-O-tert-butyl 5-O-[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (3S,4R)-4-phenyl-3-trimethylsilyl-3,4-dihydropyrazole-2,5-dicarboxylate
• CAS: 196314-29-1
• 化学式: C₃₄H₄₈N₂O₄Si
• 分子量: 576.852
• InChiKey: WYOJNQVGMCNLHH-WONAHMQBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.95
• 重原子数：
  41
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  68.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-(1R,2S,5R)-8-phenylmenthyl 3-((4R,5S)-1-tert-butoxycarbonyl-4,5-dihydro-4-phenyl-5-trimethylsilyl-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,4R,5S)-1-<(tert-butoxycarbonyl)amino>-3-(tert-butyldimethylsilyloxymethyl)-2-(ethoxycarbonyl)-4-phenyl-5-trimethylsilylpyrazolidine
  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：

  2-丙烯酸,3-苯基-,(1R,2S,5R)-5-甲基-2-(1-甲基-1-苯基乙基)环己基酯,(2E)- 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 194.0h， 生成 (-)-(1R,2S,5R)-8-phenylmenthyl 3-((4R,5S)-1-tert-butoxycarbonyl-4,5-dihydro-4-phenyl-5-trimethylsilyl-1H-pyrazole)carboxylate
  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

文献信息

• First diastereoselective [3+2] cycloaddition of chiral non-racemic alkenyl Fischer carbene complexes with diazomethane derivatives
  作者：José Barluenga、Félix Fernández-Marí、Argimiro L. Viado、Enrique Aguilar、Bernardo Olano

  DOI：10.1039/a704228k

  日期：——

  (-)-8-Phenylmenthol derived pentacarbonylalkenyl(alkoxy)chromium carbene complexes react with diazomethane derivatives to give only one diastereomer of enantiomerically pure 4,5-dihydro-1H-pyrazoles; the one-pot synthesis of the corresponding esters is also described.

  (-)-8-苯基薄荷醇衍生的五羰基烯丙基（烷氧基）碳烯铬络合物与重氮甲烷衍生物反应，仅生成一种对映纯的4,5-二氢-1H-吡唑的非对映异构体；还描述了相应酯类的一锅法合成。
• 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
  作者：José Barluenga、Félix Fernández-Marí、Argimiro L. Viado、Enrique Aguilar、Bernardo Olano、Santiago García-Granda、Carmen Moya-Rubiera

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

  日期：1999.3.1

  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.