2-(2-[1,3]Dioxolan-2-yl-ethyl)-3-oxo-butyric acid tert-butyl ester | 138606-93-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-(2-[1,3]Dioxolan-2-yl-ethyl)-3-oxo-butyric acid tert-butyl ester
• 英文别名: tert-butyl 2-[2-(1,3-dioxolan-2-yl)ethyl]-3-oxobutanoate
• CAS: 138606-93-6
• 化学式: C₁₃H₂₂O₅
• 分子量: 258.315
• InChiKey: TXZOTGVOKPWMBU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.69
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-(2-[1,3]Dioxolan-2-yl-ethyl)-3-oxo-butyric acid tert-butyl ester 在 lithium hydroxide 、 sodium hydride 、 对甲苯磺酸 作用下， 反应 26.5h， 生成 3-Benzenesulfonylmethyl-2-(2-[1,3]dioxolan-2-yl-ethyl)-cyclopent-2-enone
  参考文献：
  名称：

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes as versatile reagents for the synthesis of annulated furans and cyclopentenones

  摘要：

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes (DBP and DIP) are conveniently prepared by treating 1-(phenylsulfonyl)-1,2-propadiene with the appropriate halogen. These novel reagents undergo reaction with a variety of simple beta-dicarbonyl anions to give substituted and annulated furans. When the reaction is carried out in polar solvents, 2,3,4-trisubstituted furans are formed. The reaction proceeds by an initial addition-elimination of the carbanion onto the vinyl carbon of the unsaturated sulfone which is followed by intramolecular ring closure on the enolate oxygen atom. When sodium methoxide is used as the base, the initially produced adduct undergoes deacylation and subsequent cyclization to give a 2,4-disubstituted furan. The synthetic utility of the method is demonstrated by a synthesis of (R)-menthofuran. Treatment of DIP with various trimethylsilyl enol ethers in the presence of silver tetrafluoroborate give alkylation products derived from S(N)2 displacement of the terminal halide. These compounds readily cyclize with base to produce an isomeric set of furans. Anions derived from 1,3-dicarbonyls substituted in the C-2 position are found to induce a complete reversal in the mode of ring closure. The major products obtained are 3-[(phenylsulfonyl)methyl]-substituted cyclopentenones. The internal displacement reaction leading to the furan ring apparently encounters an unfavorable A1,3-interaction in the transition state when a substituent group is present at the 2-position of the dicarbonyl compound. This steric interaction is not present in the transition state leading to the cyclopentenone ring. An efficient synthesis of cis-jasmone was carried out using this methodology.

  DOI：

  10.1021/jo00030a025
• 作为产物：
  描述：

  2-(2-溴乙基)-1,3-二恶烷 、 乙酰乙酸叔丁酯 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 生成 2-(2-[1,3]Dioxolan-2-yl-ethyl)-3-oxo-butyric acid tert-butyl ester
  参考文献：
  名称：

  镍催化末端炔烃的不对称反选择性硼基烷基化

  摘要：

  炔三键向双键的选择性转化是构建取代烯烃的有效平台。尽管其时空调控已取得重大进展，但实现需要克服多方面选择性问题的多组分对映选择性反应仍然不常见。在这里，我们报告了通过镍催化对末端炔烃进行前所未有的不对称反立体选择性硼基碳官能化。利用廉价的手性二胺配体可以实现末端炔烃、二硼试剂和前手性烷基亲电子试剂的三组分交叉偶联，并具有高水平的区域选择性、立体选择性和对映选择性。该反应提供了一种有效的方案来获得带有α-立体中心的对映体富集的烯基酯，非常实用，并且具有广泛的范围和出色的官能团兼容性。此外，该方法的价值在后续的多种立体保留衍生化和复杂药物分子的立体选择性简明合成中也得到了凸显。

  DOI：

  10.1021/jacs.3c05969