N-tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-thiophene carboxamide | 632325-52-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: N-tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-thiophene carboxamide
• 英文别名: 2-(2-tert-butylcarboxamido-3-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；N-tert-butyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxamide
• CAS: 632325-52-1
• 化学式: C₁₅H₂₄BNO₃S
• 分子量: 309.237
• InChiKey: KGODJPLGKRYQSI-UHFFFAOYSA-N

物化性质

• 沸点：
  437.1±30.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  75.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-溴-N,N-二甲基苯胺 、 N-tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-thiophene carboxamide 在 potassium phosphate 、 二(三叔丁基膦)钯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以59%的产率得到N-tert-butyl 3-(4-(N',N'-dimethylamino)phenyl)-2-thiophene carboxamide
  参考文献：
  名称：

  Synthesis of 2,3-Substituted Thienylboronic Acids and Esters

  摘要：

  A noncryogenic protocol for the synthesis of 2-substituted 3-thienylboronic acids and esters as well as 3-substituted 2-thienylboronic acids and esters has been developed. Electrophiles were introduced regiospecifically in the 2-position of 2,3-dibromothiophene and in the 3-position of 2-bromo-3-iodothiophene by halogen-magnesium exchange followed by quenching with electrophiles. Palladium-catalyzed borylation of the 2,3-substituted halothiophenes with pinacolborane and P(t-Bu)(3) as ligand for Pd produced 9 and 10. The borylation protocol was tolerated by a range of functional groups; however, strongly electron-withdrawing substituents decreased the stability of the thienylboronic acids and esters.

  DOI：

  10.1021/jo034919n
• 作为产物：
  描述：

  叔丁基异氰酸酯 在 二(三叔丁基膦)钯 、 乙基氯化镁 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 N-tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-thiophene carboxamide
  参考文献：
  名称：

  Synthesis of 2,3-Substituted Thienylboronic Acids and Esters

  摘要：

  A noncryogenic protocol for the synthesis of 2-substituted 3-thienylboronic acids and esters as well as 3-substituted 2-thienylboronic acids and esters has been developed. Electrophiles were introduced regiospecifically in the 2-position of 2,3-dibromothiophene and in the 3-position of 2-bromo-3-iodothiophene by halogen-magnesium exchange followed by quenching with electrophiles. Palladium-catalyzed borylation of the 2,3-substituted halothiophenes with pinacolborane and P(t-Bu)(3) as ligand for Pd produced 9 and 10. The borylation protocol was tolerated by a range of functional groups; however, strongly electron-withdrawing substituents decreased the stability of the thienylboronic acids and esters.

  DOI：

  10.1021/jo034919n

文献信息

• On the Directing Effect of Boronate Groups in the Lithiation of Boronated Thiophenes
  作者：Elena Borowska、Krzysztof Durka、Sergiusz Luliński、Janusz Serwatowski、Krzysztof Woźniak

  DOI：10.1002/ejoc.201101764

  日期：2012.4

  An investigation of thiophene boronates has revealed the usefulness of a metalation reaction in the synthesis of various lithiated thiophene boronates, which were further converted to functionalized thiopheneboronic derivatives. The lithiation of 2- and 3-thienylboronic N-butyldiethanolamine (BDEA) esters with lithium diisopropylamide and lithium 2,2,6,6-tetramethylpiperidide showed that both boronated

  对噻吩硼酸酯的研究揭示了金属化反应在合成各种锂化噻吩硼酸酯中的有用性，这些锂化噻吩硼酸酯进一步转化为功能化的噻吩硼酸酯衍生物。2-和3-噻吩基硼N-丁基二乙醇胺(BDEA) 酯与二异丙基氨基锂和2,2,6,6-四甲基哌啶锂的锂化表明两种硼化噻吩都容易去质子化。在后一种情况下，由于硼烷基的显着稳定作用，与硫和硼烷基相邻的 2-位的锂化在热力学上是有利的。用一系列亲电子试剂进一步衍生，然后水解，得到各种 2-取代的 3-噻吩硼酸。[ThB(OR)3]Li 类型的相应噻吩硼酸盐“ate”配合物的锂化表明 2-噻吩衍生物不能被有效地去质子化，而“ate”配合物 [3-ThB(OEt)3]Li ，在 C-2 处用 nBuLi 选择性锂化。这表明阴离子硼酸盐部分的导向作用。得到的双金属物质 [(2-Li-3-Th)B(OEt)3]Li 在加热时发生闭环二聚反应，在随后的水解后得到 4,8-二氢-4,8-​​二羟基-p