(1R)-2-exo-trimethylsilyloxy-1,7,7-trimethylbicyclo[2.2.1]heptane-2-carbonitrile | 332920-04-4

• 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)-2-exo-trimethylsilyloxy-1,7,7-trimethylbicyclo[2.2.1]heptane-2-carbonitrile
• 英文别名: (1R,2R)-2-trimethylsilyloxy-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl-carbonitrile；2-cyano-2-trimethylsilanyloxy-1,3,3-trimethyl-[2.2.1]-bicycloheptane；(1R,2R,4R)-1,7,7-trimethyl-2-trimethylsilyloxybicyclo[2.2.1]heptane-2-carbonitrile
• CAS: 332920-04-4
• 化学式: C₁₄H₂₅NOSi
• 分子量: 251.444
• InChiKey: ZYXLSWOSEYNVLC-BNOWGMLFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.95
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  正丁基锂 、 (1R)-2-exo-trimethylsilyloxy-1,7,7-trimethylbicyclo[2.2.1]heptane-2-carbonitrile 在 溶剂黄146 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.0h， 以80%的产率得到(1R)-2-endo-pentanoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  A concise and efficient route to the Alzheimer's therapeutic agent (R)-arundic acid

  摘要：

  A short and efficient procedure for the preparation of (R)-arundic acid, a therapeutic agent for the treatment of Alzheimer's disease, has been developed. Based an cheap and commercially available (1R)-(+)-camphor as the source of chiral information, (R)-arundic acid is synthesized in a four-step cyclic sequence with 55% overall yield and high optical purity, >= 98% ee. Alkyl halide and acetylene constitute the only consumable carbon Sources of this method, which allows obtaining of both enantiomers and recycling of chiral auxiliary. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.09.026
• 作为产物：
  描述：

  三甲基氰硅烷 、 白樟油 以 四氢呋喃 为溶剂， 反应 4.0h， 以90%的产率得到(1R)-2-exo-trimethylsilyloxy-1,7,7-trimethylbicyclo[2.2.1]heptane-2-carbonitrile
  参考文献：
  名称：

  A concise and efficient route to the Alzheimer's therapeutic agent (R)-arundic acid

  摘要：

  A short and efficient procedure for the preparation of (R)-arundic acid, a therapeutic agent for the treatment of Alzheimer's disease, has been developed. Based an cheap and commercially available (1R)-(+)-camphor as the source of chiral information, (R)-arundic acid is synthesized in a four-step cyclic sequence with 55% overall yield and high optical purity, >= 98% ee. Alkyl halide and acetylene constitute the only consumable carbon Sources of this method, which allows obtaining of both enantiomers and recycling of chiral auxiliary. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.09.026

文献信息

• A New Lithium Alkoxide Accelerated Diastereoselective Cyanation of Ketones
  作者：H. Scott Wilkinson、Paul T. Grover、Charles P. Vandenbossche、Roger P. Bakale、Nandkumar N. Bhongle、Stephen A. Wald、Chris H. Senanayake

  DOI：10.1021/ol0069608

  日期：2001.2.1

  lithium heteroatom assisted TMSCN or TBSCN addition to aldehydes and ketones has been discovered. The process provides excellent selectivities and high rates. Conformationally constrained ketones such as camphor, fenchone, and nopinone give excellent diastereoselectivities with TMSCN. Reduction of 2 provided diastereopure amino alcohol 3 in good yield. alpha- and beta-Methyl cyclohexanones with TBSCN-LiOR

  [反应：见正文]已经发现，在醛和酮中添加了一种非常普通的锂杂原子辅助的TMSCN或TBSCN。该方法具有出色的选择性和高产率。构象受限制的酮，如樟脑，芬琴酮和诺品酮，与TMSCN的结合具有极好的非对映选择性。还原2以良好的产率提供了非对映体纯的氨基醇3。具有TBSCN-LiOR的α-和β-甲基环己酮具有很高的非对映选择性和收率。
• [HC(py)3W(NO)2(CO)](SbF6)2 as a Lewis acid precursor in additions of silylated C-nucleophiles to carbonyl compounds
  作者：J.W. Faller、Lise-Lotte Gundersen

  DOI：10.1016/s0040-4039(00)77592-7

  日期：1993.4

  [HC(PY)3W(NO)2(CO)](SbF6)2 is a feasible Lewis acid catalyst precursor for the addition of silylated C-nucleophiles to carbonyl compounds. The O-silylated adducts are easily isolated without aqueous wort-up and the catalyst can be recycled. A remarkable solvent effect is found in the addition of TMS-CN to cyclohexanones.
• Chiral β- and γ-aminoalcohols derived from (+)-camphor and (−)-fenchone as catalysts for the enantioselective addition of diethylzinc to benzaldehyde
  作者：Vladimir Dimitrov、Georgi Dobrikov、Miroslav Genov

  DOI：10.1016/s0957-4166(01)00221-x

  日期：2001.6

  The addition of Me3SiCN and LICH2CN to (+)-camphor and (-)-fenchone. respectively, followed by reduction leads to chiral beta- and gamma -aminoalcohols. The enantioselectivities realized using these aminoalcohols as ligands in the addition of Et2Zn to benzaldehyde were lower than those obtained using the corresponding delta -aminoalcohols. (C) 2001 Elsevier Science Ltd. All rights reserved.
• A concise and efficient route to the Alzheimer's therapeutic agent (R)-arundic acid
  作者：Jesús M. García、José M. Odriozola、Ainara Lecumberri、Jesús Razkin、Alberto González

  DOI：10.1016/j.tet.2008.09.026

  日期：2008.11

  A short and efficient procedure for the preparation of (R)-arundic acid, a therapeutic agent for the treatment of Alzheimer's disease, has been developed. Based an cheap and commercially available (1R)-(+)-camphor as the source of chiral information, (R)-arundic acid is synthesized in a four-step cyclic sequence with 55% overall yield and high optical purity, >= 98% ee. Alkyl halide and acetylene constitute the only consumable carbon Sources of this method, which allows obtaining of both enantiomers and recycling of chiral auxiliary. (C) 2008 Elsevier Ltd. All rights reserved.