3-bromo-2-t-butyldimethylsilyl-thiophene | 211737-49-4

• 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-bromo-2-t-butyldimethylsilyl-thiophene
• 英文别名: 2-TBS-3-bromothiophene；(3-Bromothiophen-2-yl)-tert-butyl-dimethylsilane
• CAS: 211737-49-4
• 化学式: C₁₀H₁₇BrSSi
• 分子量: 277.3
• InChiKey: IDPCEQKSRMSQFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  13
• 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：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  异丁醛 、 3-bromo-2-t-butyldimethylsilyl-thiophene 在 叔丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.5h， 以97%的产率得到1-[2-[Tert-butyl(dimethyl)silyl]thiophen-3-yl]-2-methylpropan-1-ol
  参考文献：
  名称：

  Solvent-Controlled C^sp2→O Silyl Migration:  The “One-Pot” Synthesis of 2,3-Disubsituted Thiophenes

  摘要：

  An effective "one-pot" synthesis of disubstituted thiophene derivatives employing 3-bromo-2-silyl thiophenes has been developed. A solvent-controlled [1,4] C-sp2 -> O silyl migration was involved as the key step in this process.

  DOI：

  10.1021/ol702149c
• 作为产物：
  描述：

  2-(叔丁基二甲基硅烷基)噻吩 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 2-bromo-5-(tert-butyldimethylsilyl)thiophene 、 3-bromo-2-t-butyldimethylsilyl-thiophene
  参考文献：
  名称：

  Oligothiophene S,S-Dioxides. Synthesis and Electronic Properties in Relation to the Parent Oligothiophenes

  摘要：

  Oligothiophene S,S-dioxides from dimers to pentamers were obtained in good yields by reaction of mono- and dibrominated thiophene S,S-dioxides with the appropriate thienyl stannanes in the presence of Pd(AsPh3)(4) generated in situ. The reaction rate with brominated thiophene S,S-dioxides is greatly accelerated compared to that employing thienyl bromides to obtain the parent oligothiophenes. HF/6-31G* ab initio calculations on 2,2'-bithiophene and the corresponding mono- and bis-S,S-dioxides show that the functionalization of the thienyl sulfur to the S,S-dioxide does not affect the pi,pi* nature of the frontier orbitals, decreases the energy of the LUMO much more than that of the HOMO, increases the degree of planarity of the molecular skeleton, and leads to higher syn anti rotation barriers about the carbon-carbon bond.

  DOI：

  10.1021/jo980507g

文献信息

• Multicomponent Type II Anion Relay Chemistry (ARC): One-Pot Syntheses of 2,3-Disubstituted Furans and Thiophenes
  作者：Nelmi O. Devarie-Baez、Won-Suk Kim、Amos B. Smith、Ming Xian

  DOI：10.1021/ol900434k

  日期：2009.4.16

  Effective, one-pot syntheses of 2,3-disubstituted furans and thiophenes, exploiting 2-tert-butyldimethylsilyl-3-formylfuran and -thiophene as the respective bifunctional linchpins, have been developed. The synthetic protocol involves multicomponent type II Anion Relay Chemistry (ARC) mediated by a solvent-controlled C(sp2)→O 1,4-Brook rearrangement. Simple organolithiums and α-disubstituted ester enolates

  利用 2-叔丁基二甲基甲硅烷基-3-甲酰基呋喃和-噻吩作为各自的双功能关键，已开发出有效的一锅法合成 2,3-二取代呋喃和噻吩。合成方案涉及多组分II型阿信联盟- [R elay Ç hemistry（ARC）通过溶剂控制的C（SP介导2）→O; 1,4-布鲁克重排。简单的有机锂和 α-二取代酯烯醇被证明是有效的引发亲核试剂。
• Oligothiophene <i>S</i>,<i>S</i>-Dioxides. Synthesis and Electronic Properties in Relation to the Parent Oligothiophenes
  作者：G. Barbarella、L. Favaretto、G. Sotgiu、M. Zambianchi、L. Antolini、O. Pudova、A. Bongini

  DOI：10.1021/jo980507g

  日期：1998.8.1

  Oligothiophene S,S-dioxides from dimers to pentamers were obtained in good yields by reaction of mono- and dibrominated thiophene S,S-dioxides with the appropriate thienyl stannanes in the presence of Pd(AsPh3)(4) generated in situ. The reaction rate with brominated thiophene S,S-dioxides is greatly accelerated compared to that employing thienyl bromides to obtain the parent oligothiophenes. HF/6-31G* ab initio calculations on 2,2'-bithiophene and the corresponding mono- and bis-S,S-dioxides show that the functionalization of the thienyl sulfur to the S,S-dioxide does not affect the pi,pi* nature of the frontier orbitals, decreases the energy of the LUMO much more than that of the HOMO, increases the degree of planarity of the molecular skeleton, and leads to higher syn anti rotation barriers about the carbon-carbon bond.
• Solvent-Controlled C^sp2→O Silyl Migration:  The “One-Pot” Synthesis of 2,3-Disubsituted Thiophenes
  作者：Nelmi O. Devarie-Baez、Brian J. Shuhler、Hua Wang、Ming Xian

  DOI：10.1021/ol702149c

  日期：2007.10.1

  An effective "one-pot" synthesis of disubstituted thiophene derivatives employing 3-bromo-2-silyl thiophenes has been developed. A solvent-controlled [1,4] C-sp2 -> O silyl migration was involved as the key step in this process.