3-Methyl-1-(trimethylsilyl)-1-pentyne | 133986-40-0

• 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: 3-Methyl-1-(trimethylsilyl)-1-pentyne
• 英文别名: Trimethyl(3-methylpent-1-ynyl)silane
• CAS: 133986-40-0
• 化学式: C₉H₁₈Si
• 分子量: 154.327
• InChiKey: SILUGGMPBUHPEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.91
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  3-Methyl-1-(trimethylsilyl)-1-pentyne 在 sodium hydroxide 、 双氧水 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 正戊烷 为溶剂， 反应 18.5h， 生成 3-Methyl-1-trimethylsilanyl-pentan-1-ol
  参考文献：
  名称：

  A simple synthesis of B-2-(1-trimethylsilyl-1-alkyl)-1,3,2-dioxaborinanes. Isolation and selective oxidation to 1-trimethylsilyl-1-alkanols

  摘要：

  (Z)-1-Trimethylsilyl-1-alkenes easily prepared by the hydroboration of the corresponding 1-trimethylsilyl-1-alkynes followed by protonolysis with acetic acid, readily react with dibromoborane-methyl sulfide complex in dichloromethane for 6 h. The resulting solution is then treated with 1,3-propane diol in a 1:1 mixture of dichloromethane and n-pentane at 0degreesC for half an hour to provide the corresponding gem-dimetalloalkanes containing boron and silicon. These alpha-trimethylsilylalkylboronate esters are purified by vacuum distillation in high yields (72-84%) and the structures of these novel intermediates are further confirmed by selective oxidation with alkaline hydrogen peroxide to provide the corresponding alcohols containing trimethylsilyl group. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01750-7
• 作为产物：
  描述：

  三甲基氯硅烷 、 3-甲基-1-戊炔 在 正丁基锂 作用下， 反应 2.0h， 生成 3-Methyl-1-(trimethylsilyl)-1-pentyne
  参考文献：
  名称：

  A simple synthesis of B-2-(1-trimethylsilyl-1-alkyl)-1,3,2-dioxaborinanes. Isolation and selective oxidation to 1-trimethylsilyl-1-alkanols

  摘要：

  (Z)-1-Trimethylsilyl-1-alkenes easily prepared by the hydroboration of the corresponding 1-trimethylsilyl-1-alkynes followed by protonolysis with acetic acid, readily react with dibromoborane-methyl sulfide complex in dichloromethane for 6 h. The resulting solution is then treated with 1,3-propane diol in a 1:1 mixture of dichloromethane and n-pentane at 0degreesC for half an hour to provide the corresponding gem-dimetalloalkanes containing boron and silicon. These alpha-trimethylsilylalkylboronate esters are purified by vacuum distillation in high yields (72-84%) and the structures of these novel intermediates are further confirmed by selective oxidation with alkaline hydrogen peroxide to provide the corresponding alcohols containing trimethylsilyl group. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01750-7

文献信息

• Preparation of 2,2-Dichloro-3(2H)-furanone and Its Reactions with Heteronucleophiles
  作者：Masahiro Murakami、Minoru Hayashi、Yoshihiko Ito

  DOI：10.1021/jo00104a058

  日期：1994.12
• 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.
• Simple procedures for the preparation of (Z)-2-(1-trimethylsilyl-1-alkenyl)-1,3,2-dioxaborinanes
  作者：Narayan G Bhat、Claudia P Aguirre

  DOI：10.1016/s0040-4039(00)01405-2

  日期：2000.10

  Two simple procedures for obtaining (Z)-2-(1-trimethylsilyl-1-alkenyl)-1,3,2-dioxaborinanes based on 1-trimethylsilyl-1-alkynes are described. In the first procedure, 1-trimethylsilyl-1-alkynes are hydroborated with diisopinocampheylborane to provide the corresponding (Z)-2-(trimethylsily1-1-alkenyl)-diisopinocampheylboranes. These are then reacted with excess acetaldehyde to afford the corresponding (2)-2-(1-trimethylsilyl-1-alkenyl)-diethoxyboranes which are esterified with 1,3-propane diol to give the (2)-2-(1-trimethylsilyl-1-alkenyl)-1,3,2-dioxaborinanes in good yields and in high stereochemical purities. In the second procedure, 1-trimethylsilyl-1-alkynes are hydroborated with dichloroborane-methyl sulfide complex in the presence of a stoichiometric amount of boron trichloride in hexane, followed by treatment with 1,3-propane diol. These novel stereodefined gem-alkenyldimetaliic compounds containing boron and silicon are isolated and characterized by NMR (H-1 and C-13) spectral data. (C) 2000 Elsevier Science Ltd. All rights reserved.
• STANG, PETER J.;KITAMURA, TSUGIO;BOEHSHAR, MANFRED;WINGERT, HORST, J. AMER. CHEM. SOC., 111,(1989) N, C. 2225-2230
  作者：STANG, PETER J.、KITAMURA, TSUGIO、BOEHSHAR, MANFRED、WINGERT, HORST

  DOI：——

  日期：——
• MARTIN, S.;SAUVETRE, R.;NORMANT, J. -F., J. ORGANOMET. CHEM., 1986, 303, N 3, 317-320
  作者：MARTIN, S.、SAUVETRE, R.、NORMANT, J. -F.

  DOI：——

  日期：——