(trimethylsilyl)((1R,2R,3R,5S)-trans-isopinocamphenyl)ethyne | 133986-38-6

• 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: (trimethylsilyl)((1R,2R,3R,5S)-trans-isopinocamphenyl)ethyne
• 英文别名: trimethyl{2-[(1R,2R,3R,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]ethynyl}silane；trimethyl-[2-[(1R,2R,3R,5S)-2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl]ethynyl]silane
• CAS: 133986-38-6
• 化学式: C₁₅H₂₆Si
• 分子量: 234.457
• InChiKey: HYRHWMOTJLODPC-REWJHTLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  (trimethylsilyl)((1R,2R,3R,5S)-trans-isopinocamphenyl)ethyne 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 (1R,2R,3R,5S)-(-)-trans-isopinocampheylethyne
  参考文献：
  名称：

  自由基介导的B-烷基儿茶酚硼烷的烯基化，炔基化，甲胺化和氰化。

  摘要：

  DOI：

  10.1002/anie.200601206
• 作为产物：
  描述：

  (+)-α-蒎烯 、 phenyl 2-(trimethylsilyl)ethynyl sulfone 在 N,N-二甲基乙酰胺 、 儿萘酚硼烷 、 di-tert-butoxydiazene 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以72%的产率得到(trimethylsilyl)((1R,2R,3R,5S)-trans-isopinocamphenyl)ethyne
  参考文献：
  名称：

  自由基介导的B-烷基儿茶酚硼烷的烯基化，炔基化，甲胺化和氰化。

  摘要：

  DOI：

  10.1002/anie.200601206

文献信息

• Chiral synthesis via organoboranes. 29. A general synthesis of .alpha.-chiral monosubstituted acetylenes and their trimethylsilyl derivatives from enantiomerically pure boronic esters
  作者：Herbert C. Brown、Verinder K. Mahindroo、N. G. Bhat、Bakthan Singaram

  DOI：10.1021/jo00004a030

  日期：1991.2

  The procedure for the synthesis of RC = CH by the iodination of [R3BC = CH]-Li+ is impractical for the synthesis of the corresponding chiral derivatives, R*C = CH, due to the unavailability of the required R*3B compounds. RThxBOMe and R*ThxBOCH3, now readily available by established procedures, serve handily for the syntheses of RC = CR' and R*C = CR respectively from LiC = CR, but fail for the syntheses of either RC = CH or R*C = CH, in reasonable yield, from LiC = CH. Fortunately, this difficulty can be circumvented by utilizing LiC = CSiMe3. Indeed, treatment of enantiomerically pure monoalkylthexylborinates, R*ThxBOCH3, readily prepared from enantionerically pure boronic esters, with LiC = CSiMe3 forms an ate complex which readily undergoes the desired iodine-induced rearrangement, forming alpha-chiral (trimethylsilyl)acetylenes, R*C = CSiMe3. The (trimethylsilyl)acetylenes are easily desilylated to afford the corresponding alpha-chiral terminal acetylenes, R*C = CH, in yields of approximately 70% and essentially 100% enantiomeric excess (greater-than-or-equal-to 99%). These intermediates, R*C = CSiMe3 and R*C = CH, can be readily converted by simple procedures into a wide variety of pure enantiomers: R*CH = CH2, R*CH2CHO, R*CO2H, R*CH2CO2H, R*COCO2R, etc. Since both (+)- and (-)-alkylboronic esters are now readily available in essentially 100% enantiomeric purity, it is now possible to synthesize (+)- and (-)-alpha-chiral monosubstituted acetylenes and their trimethylsilyl derivatives in very high enantiomeric purities. This provides the first general, efficient synthesis of these valuable synthons in such high enantiomeric purities.
• BROWN, HERBERT C.;MAHINDROO, VERINDER K.;BHAT, N. G.;SINGARAM, BAKTHAN, J. ORG. CHEM., 56,(1991) N, C. 1500-1505
  作者：BROWN, HERBERT C.、MAHINDROO, VERINDER K.、BHAT, N. G.、SINGARAM, BAKTHAN

  DOI：——

  日期：——
• Radical-Mediated Alkenylation, Alkynylation, Methanimination, and Cyanation ofB-Alkylcatecholboranes
  作者：Arnaud-Pierre Schaffner、Vincent Darmency、Philippe Renaud

  DOI：10.1002/anie.200601206

  日期：2006.9.4