(2S,5S)-1,6-Bis<(tert-butyldimethylsilyl)oxy>-2,5-hexanediol | 131618-28-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2S,5S)-1,6-Bis<(tert-butyldimethylsilyl)oxy>-2,5-hexanediol
• 英文别名: (2S,5S)-1,6-bis[[tert-butyl(dimethyl)silyl]oxy]hexane-2,5-diol
• CAS: 131618-28-5
• 化学式: C₁₈H₄₂O₄Si₂
• 分子量: 378.7
• InChiKey: RWYFELQNGQNQJI-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  24
• 可旋转键数：
  11
• 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,5S)-1,6-Bis<(tert-butyldimethylsilyl)oxy>-2,5-hexanediol 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 [(2R,5R)-1-[2-[(2R,5R)-2,5-bis[[tert-butyl(dimethyl)silyl]oxymethyl]phospholan-1-yl]phenyl]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]phospholan-2-yl]methoxy-tert-butyl-dimethylsilane
  参考文献：
  名称：

  Synthesis, Characterization, and Applicability of Neutral Polyhydroxy Phospholane Derivatives and Their Rhodium(I) Complexes for Reactions in Organic and Aqueous Media

  摘要：

  Two different protocols for the preparation of water-soluble, enantiomerically pure polyhydroxybisphospholanes from acid-labile acetal and tert-butyldimethylsilyl-protected derivatives are reported. These procedures circumvent two of the commonly encountered limitations in the synthesis of these potentially important ligands: (a) formation of phosphonium salts from the highly basic phosphine under acidic conditions, and (b) the need to start with preformed, fully protected cationic metal complex. Thus, cationic Rh complexes of these ligands have been prepared in a separate step, and they have been found to be excellent catalysts for organic and aqueous phase hydrogenation of dehydroamino acids. The viability of catalyst recovery has been demonstrated in three different systems, including two cases where > 99% ee can be achieved under recycling conditions.

  DOI：

  10.1021/ja011500a
• 作为产物：
  描述：

  1,2,5,6-四羟基己烷 、 叔丁基二甲基氯硅烷 生成 (2S,5S)-1,6-Bis<(tert-butyldimethylsilyl)oxy>-2,5-hexanediol
  参考文献：
  名称：

  MACHINAGA, NOBUO;KIBAYASHI, CHIHIRO, J. ORG. CHEM., 56,(1991) N, C. 1386-1393

  摘要：

  DOI：

文献信息

• Enantiodivergent total synthesis of naturally occurring trans-2-butyl-5-pentylpyrrolidine
  作者：Nobuo Machinaga、Chihim Kibayashi

  DOI：10.1016/s0040-4039(00)94464-2

  日期：1990.1

  The enantiodivergent total synthesis of (+)-(2S,5S)- and (−)-(2R,SR)-trans-2-butyl-5-pentylpyrrolidines was effected from the C2 symmetric (S,S)- and (R,R)-diepoxides, respectively, both prepared from Dmannitol, by a sequence involving stereo-defined ring construction of the unsymmetrical trans-2,5-dialkylpyrrolidine via the cyclic sulfate as a key step.

  （+）-（2 S，5 S）-和（-）-（2 R，S R）-反式-2-丁基-5-戊基吡咯烷的对映体总合成是由C 2对称的（S，S分别由D甘露醇制备的）-和（R，R）-二环氧化合物是通过涉及经由环硫酸盐的不对称反式-2,5-二烷基吡咯烷的立体定义的环结构的序列作为关键步骤的。
• Enantioselective total synthesis of (+)- and (-)-pyrrolidine 197B, a new class of alkaloid from the dendrobatid poison frog: assignment of the absolute configuration
  作者：Nobuo Machinaga、Chihiro Kibayashi

  DOI：10.1021/jo00004a011

  日期：1991.2

  Enantioselective total synthesis of both enantiomers of pyrrolidine 197B (1), a new class of dendrobatid alkaloid, is described. The synthesis begins with the C2 symmetric S,S or R,R diepoxides 4, derived from (S,S)-1,2,5,6-hexanetetraol (2) as a single common chiral synthon, and involves pyrrolidine formation via the cyclic sulfonates to afford (+)- or (-)-1, respectively. The (+) and (-) enantiomers of 1 were converted to the corresponding N-benzoyl derivatives (+)-27 and (-)-27, which were directly compared with 27 derived from natural 1 by HPLC using a Chiralcel column. This comparison established the absolute stereochemistry of the natural enantiomer of pyrrolidine 197B as 2S,5S [(+)-1].
• MACHINAGA, NOBUO;KIBAYASHI, CHIHIRO, J. ORG. CHEM., 56,(1991) N, C. 1386-1393
  作者：MACHINAGA, NOBUO、KIBAYASHI, CHIHIRO

  DOI：——

  日期：——
• Synthesis, Characterization, and Applicability of Neutral Polyhydroxy Phospholane Derivatives and Their Rhodium(I) Complexes for Reactions in Organic and Aqueous Media
  作者：T. V. RajanBabu、Yuan-Yong Yan、Seunghoon Shin

  DOI：10.1021/ja011500a

  日期：2001.10.1

  Two different protocols for the preparation of water-soluble, enantiomerically pure polyhydroxybisphospholanes from acid-labile acetal and tert-butyldimethylsilyl-protected derivatives are reported. These procedures circumvent two of the commonly encountered limitations in the synthesis of these potentially important ligands: (a) formation of phosphonium salts from the highly basic phosphine under acidic conditions, and (b) the need to start with preformed, fully protected cationic metal complex. Thus, cationic Rh complexes of these ligands have been prepared in a separate step, and they have been found to be excellent catalysts for organic and aqueous phase hydrogenation of dehydroamino acids. The viability of catalyst recovery has been demonstrated in three different systems, including two cases where > 99% ee can be achieved under recycling conditions.