分子间和分子内 Mitsunobu 反应及金属络合研究：S-氨基酸衍生的手性 1,2,3,4-四氢喹喔啉、苯并稠合[9]-N3 全氮杂、[12]-N4 全氮杂大环的合成。
Inter- and intramolecular Mitsunobu reaction and metal complexation study: synthesis of S-amino acids derived chiral 1,2,3,4-tetrahydroquinoxaline, benzo-annulated [9]-N3 peraza, [12]-N4 peraza-macrocycles.
机构信息
Medicinal and Process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow, 226001 UP, India.
出版信息
Org Biomol Chem. 2012 Feb 28;10(8):1553-64. doi: 10.1039/c1ob06304a. Epub 2012 Jan 6.
Substituted 1,2,3,4-tetrahydroquinoxaline, benzo-annulated unsymmetrical chiral [9]-N(3) peraza, and [12]-N(4) peraza-macrocycles have been synthesized employing an inter- and intramolecular Mitsunobu reaction from an amino acid derived common synthetic intermediate 3. The metal complexation study of these macrocycles has been investigated by UV-visible spectroscopic technique with binding constant (K(b)) value 1.84 × 10(3) dm(3) mol(-1) using the Benesi-Hildebrand equation and a Gibbs free energy (ΔG) -19.4 kJ mol(-1) at 35 °C for 14d with Co(2+). The binding properties of the metal were dependent on the structure of polyaza-macrocycles that were confirmed by the DFT optimized structure of two macrocycles. A detailed investigaton of UV-visible spectra of macrocycles and their complete interpretation with the help of TD-DFT along with the frontier molecular orbital calculations are presented.
取代的 1,2,3,4-四氢喹喔啉、苯并稠合不对称手性[9]-N(3) 过氮杂、[12]-N(4) 过氮杂大环通过氨基酸衍生的常见合成中间体 3 中的分子间和分子内 Mitsunobu 反应进行合成。使用 Benesi-Hildebrand 方程，通过紫外可见光谱技术研究了这些大环的金属络合特性，结合常数 (K(b)) 值为 1.84 × 10(3) dm(3) mol(-1)，在 35 °C 下，与 Co(2+) 络合 14d 后得到 Gibbs 自由能 (ΔG) -19.4 kJ mol(-1)。金属的结合性质取决于多氮杂大环的结构，这通过两个大环的 DFT 优化结构得到了证实。详细研究了大环的紫外可见光谱，并通过 TD-DFT 以及前沿分子轨道计算对其进行了全面解释。
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