(R)-2-<(trimethylsilyl)ethynyl>-2-cyclopenten-1-ol | 135040-98-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-2-<(trimethylsilyl)ethynyl>-2-cyclopenten-1-ol
• 英文别名: (+)-2-trimethylsilylethynyl-2-cyclopentenol；(R)-2-((Trimethylsilyl)ethynyl)cyclopent-2-en-1-ol；(1R)-2-(2-trimethylsilylethynyl)cyclopent-2-en-1-ol
• CAS: 135040-98-1
• 化学式: C₁₀H₁₆OSi
• 分子量: 180.322
• InChiKey: IQRTXMCOXBZWQQ-SNVBAGLBSA-N

物化性质

• 沸点：
  249.7±40.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-2-<(trimethylsilyl)ethynyl>-2-cyclopenten-1-ol 在 咪唑 、 叔丁基过氧化氢 、 三氢化钐 、 lithium aluminium tetrahydride 、 正丁基锂 、 selenium(IV) oxide 、 potassium tert-butylate 、 sodium methylate 、 sodium carbonate 、 pyridinium chlorochromate 、 mercury dichloride 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.83h， 生成 <1R-<1α(R*),3aβ,4α<(E)-(1S*,3S*,5R*)>,7aα>>-1-<1,5-dimethyl-5-<(trimethylsilyl)oxy>hexyl>-4-<2-<3-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylenebicyclo<3.1.0>hexan-1-yl>ethenyl>octahydro-7a-methyl-1H-inden-4-ol
  参考文献：
  名称：

  Convergent Synthesis of Vitamin D₃ Metabolites. Control of the Stereoselectivity in Samarium-Induced Cyclopropanations of Cyclopentenes

  摘要：

  The 25-hydroxy and 1 alpha,25-dihydroxy vitamin D-3 metabolites are obtained by solvolytic rearrangements of the 1-desoxy and 1 alpha-hydroxy cyclopropyl vinylogous alcohols 31 and 29, respectively, with simultaneous formation of the vitamin D structural triene and the 3-hydroxy function. Two complementary methods have been employed to direct the stereoselectivity ofthe samarium induced olefin cyclopropanations which ultimately lead to key chiral ring A precursors. One protocol uses the two stereogenic centers of the (R,R)-B,S-butanediol ketal moiety of 8, while the other method uses the allylic hydroxyl group of(R)-16.

  DOI：

  10.1021/jo951229d
• 作为产物：
  描述：

  [(1R)-2-(2-trimethylsilylethynyl)cyclopent-2-en-1-yl] acetate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到(R)-2-<(trimethylsilyl)ethynyl>-2-cyclopenten-1-ol
  参考文献：
  名称：

  Enantiocomplementary preparation of optically pure 2-trimethylsilylethynyl-2-cyclopentenol by homochiralization of racemic precursors: a new route to the key intermediate of 1,25-dihydroxycholecalciferol and vincamine

  摘要：

  Treatment of racemic 2-trimethylsilylethynyl-2-cyclopentenol [(+/-)-1] with vinyl acetate in the presence of lipase PS in toluene yielded a 1:1 mixture of the unreacted (S)-alcohol [(S)-1] and the (R)-acetate [(R)-7] which without isolation afforded the chirally homogeneous (R)-alcohol [(R)-1] in 73% overall yield on reaction with acetic acid in the same reaction medium in the presence of diisopropyl azodicarboxylate and triphenylphosphine, followed by reductive deacylation of the resulting (R)-acetate [(R)-7]. On the other hand, hydrolysis of the racemic acetate [(+/-)-7], obtained from [(+/-)-1], in a phosphate buffer solution in the presence of lipase PS yielded a 1:1 mixture of the (R)-alcohol [(R)-1] and the unreacted (S)-acetate [(S)-7] which without separation, furnished the enantiomerically homogeneous (S)-alcohol [(S)-1] in 75% overall yield on treatment with acetic acid under the above Mitsunobu conditions, followed by reductive deacylation of the resulting (S)-acetate [(S)-7].

  DOI：

  10.1016/s0957-4166(00)80151-2

文献信息

• Total Synthesis of Rubriflordilactone A
  作者：Jian Li、Peng Yang、Ming Yao、Jun Deng、Ang Li

  DOI：10.1021/ja5092563

  日期：2014.11.26

  The first and asymmetric total synthesis of rubriflordilactone A, a bisnortriterpenoid isolated from Schisandra rubriflora, has been accomplished in a convergent manner. Two enantioenriched fragments were forged together to give a functionalized cis-triene. A 6π-electrocyclization/aromatization sequence assembled the penta-substituted arene, and a formal vinylogous Mukaiyama aldol reaction introduced

  首次和不对称全合成 rubriflordilactone A，一种从五味子中分离的双降三萜，已经以收敛的方式完成。两个对映体富集的片段被锻造在一起以得到官能化的顺式三烯。6π-电环化/芳构化序列组装了五取代芳烃，并且正式的乙烯基向山羟醛反应引入了丁烯内酯侧链。
• Control of stereoselectivity in samarium metal induced cyclopropanations. Synthesis of 1,25-dihydroxycholecalciferol
  作者：M. Kabat、J. Kiegiel、N. Cohen、K. Toth、P.M. Wovkulich、M.R. Uskoković

  DOI：10.1016/s0040-4039(00)79919-9

  日期：1991.5

  1,25-Dihydroxycholecalciferol (23) was synthesized from A-ring precursor 18 and Windaus-Grundmann ketone 19 via cyclovitamin D 21. Key reactions include highly stereoselective (5 to 6) and stereospecific (13 to 14) cyclopropanations.
• Convergent Synthesis of Vitamin D₃ Metabolites. Control of the Stereoselectivity in Samarium-Induced Cyclopropanations of Cyclopentenes
  作者：M. M. Kabat、J. Kiegiel、N. Cohen、K. Toth、P. M. Wovkulich、M. R. Uskoković

  DOI：10.1021/jo951229d

  日期：1996.1.1

  The 25-hydroxy and 1 alpha,25-dihydroxy vitamin D-3 metabolites are obtained by solvolytic rearrangements of the 1-desoxy and 1 alpha-hydroxy cyclopropyl vinylogous alcohols 31 and 29, respectively, with simultaneous formation of the vitamin D structural triene and the 3-hydroxy function. Two complementary methods have been employed to direct the stereoselectivity ofthe samarium induced olefin cyclopropanations which ultimately lead to key chiral ring A precursors. One protocol uses the two stereogenic centers of the (R,R)-B,S-butanediol ketal moiety of 8, while the other method uses the allylic hydroxyl group of(R)-16.
• Enantiocomplementary preparation of optically pure 2-trimethylsilylethynyl-2-cyclopentenol by homochiralization of racemic precursors: a new route to the key intermediate of 1,25-dihydroxycholecalciferol and vincamine
  作者：Seiichi Takano、Mahito Suzuki、Kunio Ogasawara

  DOI：10.1016/s0957-4166(00)80151-2

  日期：1993.5

  Treatment of racemic 2-trimethylsilylethynyl-2-cyclopentenol [(+/-)-1] with vinyl acetate in the presence of lipase PS in toluene yielded a 1:1 mixture of the unreacted (S)-alcohol [(S)-1] and the (R)-acetate [(R)-7] which without isolation afforded the chirally homogeneous (R)-alcohol [(R)-1] in 73% overall yield on reaction with acetic acid in the same reaction medium in the presence of diisopropyl azodicarboxylate and triphenylphosphine, followed by reductive deacylation of the resulting (R)-acetate [(R)-7]. On the other hand, hydrolysis of the racemic acetate [(+/-)-7], obtained from [(+/-)-1], in a phosphate buffer solution in the presence of lipase PS yielded a 1:1 mixture of the (R)-alcohol [(R)-1] and the unreacted (S)-acetate [(S)-7] which without separation, furnished the enantiomerically homogeneous (S)-alcohol [(S)-1] in 75% overall yield on treatment with acetic acid under the above Mitsunobu conditions, followed by reductive deacylation of the resulting (S)-acetate [(S)-7].