(1R-cis)-trimethyl<(2-methylenebicyclo<3.1.0>hexyl)ethynyl>silane | 135041-01-9

• 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: (1R-cis)-trimethyl<(2-methylenebicyclo<3.1.0>hexyl)ethynyl>silane
• 英文别名: trimethyl-[2-[(1R,5R)-2-methylidene-1-bicyclo[3.1.0]hexanyl]ethynyl]silane
• CAS: 135041-01-9
• 化学式: C₁₂H₁₈Si
• 分子量: 190.36
• InChiKey: SEVOZODDFCSLAK-VXGBXAGGSA-N

物化性质

• 沸点：
  206.7±10.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1R-cis)-trimethyl<(2-methylenebicyclo<3.1.0>hexyl)ethynyl>silane 在 咪唑 、 叔丁基过氧化氢 、 正丁基锂 、 selenium(IV) oxide 、 三乙基硼氢化锂 作用下， 以 二氯甲烷 为溶剂， 反应 25.08h， 生成 <1R-<1α(R*),3aβ,4α(1S*,3S*,5S*),7aα>>-4-<<3-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-2-methylenebicyclo<3.1.0>hexan-1-yl>ethynyl>octahydro-7a-methyl-1-<1,5,5-trimethyl-5-((trimethylsilyl)oxy)pentyl>-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：

  -1-<(trimethylsilyl)ethynyl>bicyclo<3.1.0>hexan-2-ol 在 potassium tert-butylate 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成 (1R-cis)-trimethyl<(2-methylenebicyclo<3.1.0>hexyl)ethynyl>silane
  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

文献信息

• Total synthesis of 25-Hydroxy-16,23E-diene Vitamin D3 and 1α,25-Dihydroxy-16,23E-diene Vitamin D3: separation of genomic and nongenomic vitamin D Activities
  作者：Marek M. Kabat、Walter Burger、Sandra Guggino、Bernard Hennessy、Jerome A. Iacobelli、Kazuhiro Takeuchi、Milan R. Uskokovic

  DOI：10.1016/s0968-0896(98)00164-3

  日期：1998.11

  Separation of genomic and nongenomic vitamin D activities was achieved by structural modification of 1,25-dihydroxy vitamin D3 by introduction of 16 and 23E double bonds. The modified compound 3, lacking a 1 alpha-hydroxy group, exhibits only nongenomic activity. Its 1 alpha-hydroxy relative 4 expresses fully both genomic and non-genomic activities. A total synthesis of analogues 3 and 4 is described

  基因组和非基因组维生素D活性的分离是通过引入16和23E双键对1,25-二羟基维生素D3进行结构修饰而实现的。缺少1个α-羟基的改性化合物3仅表现出非基因组活性。它的1个α-羟基相对分子4完全表达基因组和非基因组活性。描述了类似物3和4的总合成。
• 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.