2-(tert-Butyl-dimethyl-silanyl)-furan-3-carboxylic acid | 133620-36-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 英文名称: 2-(tert-Butyl-dimethyl-silanyl)-furan-3-carboxylic acid
• 英文别名: 2-[Tert-butyl(dimethyl)silyl]furan-3-carboxylic acid
• CAS: 133620-36-7
• 化学式: C₁₁H₁₈O₃Si
• 分子量: 226.348
• InChiKey: DGINZSUPJGGKJQ-UHFFFAOYSA-N

物化性质

• 沸点：
  285.1±25.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  50.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(tert-Butyl-dimethyl-silanyl)-furan-3-carboxylic acid 在 六甲基磷酰三胺 、 正丁基锂 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 4-甲基-3-呋喃甲酸
  参考文献：
  名称：

  Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2.¹ Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings

  摘要：

  A new method for the preparation of 3,4- and 2,5-disubstituted furan rings is described. A variety of 2-silylated-3-(hydroxymethyl)furans and 2-silylated-3-furoic acids lithiate exclusively at C-4 when treated with 2.2 equivs of BuLi. The resulting dianions were quenched with a variety of electrophiles to provide 2-silylated-3-(hydroxymethyl)-substituted furans and 2-silylated-4-substituted 3-furoic acids in good to excellent yields. Removal of the silyl group (n-Bu4NF) provided a variety of 4-substituted-3-(hydroxymethyl)furans and methyl 4-substituted-3-furoates, respectively. The latter esters were prepared due to difficulties encountered in isolating 4-substituted-3-furoic acids. The site of lithiation was altered by protecting the 3-hydroxyl group with a triethylsilane. Lithiation of 2-silylated-3-(((triethylsilyl)oxy)methyl)furan with 1.2 equivs of BuLi followed by the addition of electrophiles provided 2-silylated-3-(((triethylsilyl)oxy)methyl)-5-substituted furan rings. Subsequent removal of both silyl groups provided 2,4-disubstituted furan rings in moderate to good yields. A rationale is provided to explain why protection of the hydroxyl group at C-3 leads to a change in lithiation from the C-4 to the C-5 position of the furan ring. In addition, an explanation for the observed effect of adding HMPA or LiCl to the solution during the lithiation of 2-(tert-butyldimethylsilyl)-3-(hydroxymethyl)furan is provided.

  DOI：

  10.1021/jo971098b
• 作为产物：
  描述：

  3-糠酸 在 咪唑 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.25h， 生成 2-(tert-Butyl-dimethyl-silanyl)-furan-3-carboxylic acid
  参考文献：
  名称：

  Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 1. [1,4] O → C and [1,4] C → O Silyl Migrations of Silyl Ethers and Esters Attached to Furan and Thiophene Rings

  摘要：

  [1,4] O --> C and [1,4] C --> O rearrangements are described for a variety of furans and thiophenes. Treatment of 3-((silyloxy)methyl)furans and -thiophenes with n-BuLi in HMPA provided 2-silylated-3-(hydroxymethyl)furans and -thiophenes in good to excellent yields. The reaction was shown by crossover studies to proceed via an intramolecular [1,4] O --> C silyl migration. Silyl esters of 3-furoic acids also underwent an intramolecular [1,4] O --> C silyl migration to provide 2-silylated-3-furoic acids in moderate to good yield when treated with a mixture of LDA and HMPA. Finally, the above silyl migrations were shown to be reversible. Treatment of 2-silylated-3-(hydroxymethyl)furans and -thiophenes with NaH in DMF provided 3-((silyloxy)methyl)furans and -thiophenes in excellent yields via a [1,4] C --> O silyl migration. The [1,4] C --> O silyl migration was also shown to be an intramolecular process by a crossover study.

  DOI：

  10.1021/jo971097j

文献信息

• Rapid Access to Tetracyclic Core of Wortmannin via an Intramolecular Reductive Olefin Coupling Strategy
  作者：Ying Hu、Miao Bai、Ying Yang、Jiangyan Tian、Qianghui Zhou

  DOI：10.1021/acs.orglett.0c02135

  日期：2020.8.21

  A convergent approach to assemble the fused BCDE tetracyclic framework of wortmannin is presented. This route features a very challenging Suzuki–Miyaura coupling to prepare the fully functionalized furan intermediate, a Negishi-type acylation to unite the two enantio-enriched fragments, and a subsequent hydrogen-atom-transfer-initiated 6-endo radical cyclization to install the central cyclohexadienone

  提出了一种融合的方法来组装渥曼青霉素的稠密BCDE四环骨架。这条路线的特点是极富挑战性的Suzuki-Miyaura偶联制备完全功能化的呋喃中间体，Negishi型酰化作用将两个对映体富集的片段结合在一起，随后进行氢原子转移引发的6-内基自由基环化来安装中央环己二烯酮部分，可建立C10全碳四元立体中心。
• Synthesis of α- alkoxysilanes: Birch reduction of 2-trialkylsilylfurans
  作者：Roy L. Beddoes、Mark L. Lewis、Philip Gilbert、Peter Quayle、Simon P. Thompson、Shouming Wang、Keith Mills

  DOI：10.1016/s0040-4039(96)02101-6

  日期：1996.12

  The Birch reduction of (2 -trialkysilyl)furan-3-carboxylic acids has been applied to the synthesis of methyl (2-trialkylsilyl)tetrahydrofuran-3-carboxylates. It is believed that the silicon moiety in such substrates controls the sense of asymmetric induction observed in Michael reaction of the derived enolates with methyl cinnamate. Mild oxidative removal of the silicon moiety generates an oxonium

  （2-三烷基甲硅烷基）呋喃-3-羧酸的桦木还原已被用于合成（2-三烷基甲硅烷基）四氢呋喃-3-羧酸甲酯。据信，这种底物中的硅部分控制了在衍生的烯醇化物与肉桂酸甲酯的迈克尔反应中观察到的不对称感应的感觉。硅部分的轻度氧化去除会生成氧鎓阳离子，其经过亲核捕获以提供功能化的呋喃并吡喃。
• Yu, Shuyuan; Keay, Brian A., Journal of the Chemical Society. Perkin transactions I, 1991, # 4, p. 2600 - 2601
  作者：Yu, Shuyuan、Keay, Brian A.

  DOI：——

  日期：——
• Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 2.¹ Regioselective Lithiation of 2-Silylated-3-substituted Furan Rings
  作者：Edward Bures、James A. Nieman、Shuyuan Yu、Patrick G. Spinazzé、Jean-Louis J. Bontront、Ian R. Hunt、Arvi Rauk、Brian A. Keay

  DOI：10.1021/jo971098b

  日期：1997.12.1

  A new method for the preparation of 3,4- and 2,5-disubstituted furan rings is described. A variety of 2-silylated-3-(hydroxymethyl)furans and 2-silylated-3-furoic acids lithiate exclusively at C-4 when treated with 2.2 equivs of BuLi. The resulting dianions were quenched with a variety of electrophiles to provide 2-silylated-3-(hydroxymethyl)-substituted furans and 2-silylated-4-substituted 3-furoic acids in good to excellent yields. Removal of the silyl group (n-Bu4NF) provided a variety of 4-substituted-3-(hydroxymethyl)furans and methyl 4-substituted-3-furoates, respectively. The latter esters were prepared due to difficulties encountered in isolating 4-substituted-3-furoic acids. The site of lithiation was altered by protecting the 3-hydroxyl group with a triethylsilane. Lithiation of 2-silylated-3-(((triethylsilyl)oxy)methyl)furan with 1.2 equivs of BuLi followed by the addition of electrophiles provided 2-silylated-3-(((triethylsilyl)oxy)methyl)-5-substituted furan rings. Subsequent removal of both silyl groups provided 2,4-disubstituted furan rings in moderate to good yields. A rationale is provided to explain why protection of the hydroxyl group at C-3 leads to a change in lithiation from the C-4 to the C-5 position of the furan ring. In addition, an explanation for the observed effect of adding HMPA or LiCl to the solution during the lithiation of 2-(tert-butyldimethylsilyl)-3-(hydroxymethyl)furan is provided.
• Regioselective Preparation of 2,4-, 3,4-, and 2,3,4-Substituted Furan Rings. 1. [1,4] O → C and [1,4] C → O Silyl Migrations of Silyl Ethers and Esters Attached to Furan and Thiophene Rings
  作者：Edward Bures、Patrick G. Spinazzé,、Giovanna Beese、Ian R. Hunt、Christine Rogers、Brian A. Keay

  DOI：10.1021/jo971097j

  日期：1997.12.1

  [1,4] O --> C and [1,4] C --> O rearrangements are described for a variety of furans and thiophenes. Treatment of 3-((silyloxy)methyl)furans and -thiophenes with n-BuLi in HMPA provided 2-silylated-3-(hydroxymethyl)furans and -thiophenes in good to excellent yields. The reaction was shown by crossover studies to proceed via an intramolecular [1,4] O --> C silyl migration. Silyl esters of 3-furoic acids also underwent an intramolecular [1,4] O --> C silyl migration to provide 2-silylated-3-furoic acids in moderate to good yield when treated with a mixture of LDA and HMPA. Finally, the above silyl migrations were shown to be reversible. Treatment of 2-silylated-3-(hydroxymethyl)furans and -thiophenes with NaH in DMF provided 3-((silyloxy)methyl)furans and -thiophenes in excellent yields via a [1,4] C --> O silyl migration. The [1,4] C --> O silyl migration was also shown to be an intramolecular process by a crossover study.