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Metal-free catalytic activation and borylation of the – –H bond of 1-methyl pyrrole using adamantane-derived aminoborane frustrated Lewis pairs: A density functional theory study
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2021-05-24 , DOI: 10.1002/poc.4250 Tulsi R. Patel 1, 2 , Bishwajit Ganguly 1, 2
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2021-05-24 , DOI: 10.1002/poc.4250 Tulsi R. Patel 1, 2 , Bishwajit Ganguly 1, 2
Affiliation
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Frustrated Lewis pair (FLP) chemistry has developed as a novel strategy for catalysis in organic chemistry and opened a new metal-free organic catalysis area for synthesizing various compounds of interest. Adamantane as molecular scaffolds used to design new sets of FLPs (ambiphilic molecules) for the –
–H activation and subsequent borylation of 1-methyl pyrrole employing DFT (wB97XD/6-31 + G (d,p)) level of theory. The saturated hydrocarbon showed improvement in the energetics of –
–H activation and subsequent borylation of 1-methyl pyrrole compared with the unsaturated phenylene FLPs employed for such reactions. The Lewis acid and Lewis base characters are augmented with adamantyl-derived FLPs, and the monomers responsible for the catalytic activity are also energetically more stable compared with their corresponding dimers. The H2 extrusion and the electrophilic borylation steps are energetically comparable on the Gibbs free energy surface in cases of 1-NMe2-2-BH2-C6H4 (I) and 1-Pip-2-BH2-C6H4 (II). The relative free energy barriers of activations of such steps have been significantly lowered with adamantyl scaffold FLPs by ~5.5 and ~3.7 kcal/mol for 1-NMe2-2-BH2-4-F-C10H13 (B) and ~5.6 and ~4.9 kcal/mol for 1-Pip-2-BH2-4-F-C10H13 (D), respectively. The enhanced reactivity of adamantyl FLPs has been rationalized with a molecular electrostatic potential (MESP) study. The nucleophilic and electrophilic characters of Lewis base and Lewis acid have been calculated using the conceptual density functional theory (CDFT) that support the results of the MESP study. The saturated scaffold FLPs can be promising candidates to improve the efficiency of catalysts in many reactions.
中文翻译：
使用金刚烷衍生的氨基硼烷挫败路易斯对对 1-甲基吡咯的 – –H 键进行无金属催化活化和硼化：密度泛函理论研究
受挫路易斯对 (FLP) 化学已发展成为有机化学催化的新策略，并为合成各种感兴趣的化合物开辟了一个新的无金属有机催化领域。金刚烷作为分子支架，用于设计新的 FLP（两亲分子）组，用于使用 DFT (wB97XD/6-31 + G (d,p)) 理论水平的 –
H 活化和随后的 1-甲基吡咯硼化。饱和烃显示出以下能量学的改善 -
与用于此类反应的不饱和亚苯基 FLP 相比，1-甲基吡咯的 –H 活化和随后的硼化。金刚烷基衍生的 FLP 增强了路易斯酸和路易斯碱的特性，与相应的二聚体相比，负责催化活性的单体在能量上也更加稳定。在 1-NMe 2 -2-BH 2 -C 6 H 4 (I)和 1-Pip-2-BH 2 -C 6 的情况下，H 2挤出和亲电硼化步骤在吉布斯自由能表面上的能量相当H 4 (II) . 对于 1-NMe 2 -2-BH 2 -4-FC 10 H 13 (B)和 ~5.6 的金刚烷基支架 FLP，这些步骤激活的相对自由能垒已显着降低 ~5.5 和 ~3.7 kcal/mol 1-Pip-2-BH 2 -4-FC 10 H 13 (D) ~4.9 kcal/mol， 分别。金刚烷基 FLP 的增强反应性已通过分子静电势 (MESP) 研究得到合理化。使用支持 MESP 研究结果的概念密度泛函理论 (CDFT) 计算了路易斯碱和路易斯酸的亲核和亲电特征。饱和支架 FLP 可以成为提高催化剂在许多反应中效率的有希望的候选者。
更新日期：2021-05-24
–H activation and subsequent borylation of 1-methyl pyrrole employing DFT (wB97XD/6-31 + G (d,p)) level of theory. The saturated hydrocarbon showed improvement in the energetics of –
–H activation and subsequent borylation of 1-methyl pyrrole compared with the unsaturated phenylene FLPs employed for such reactions. The Lewis acid and Lewis base characters are augmented with adamantyl-derived FLPs, and the monomers responsible for the catalytic activity are also energetically more stable compared with their corresponding dimers. The H2 extrusion and the electrophilic borylation steps are energetically comparable on the Gibbs free energy surface in cases of 1-NMe2-2-BH2-C6H4 (I) and 1-Pip-2-BH2-C6H4 (II). The relative free energy barriers of activations of such steps have been significantly lowered with adamantyl scaffold FLPs by ~5.5 and ~3.7 kcal/mol for 1-NMe2-2-BH2-4-F-C10H13 (B) and ~5.6 and ~4.9 kcal/mol for 1-Pip-2-BH2-4-F-C10H13 (D), respectively. The enhanced reactivity of adamantyl FLPs has been rationalized with a molecular electrostatic potential (MESP) study. The nucleophilic and electrophilic characters of Lewis base and Lewis acid have been calculated using the conceptual density functional theory (CDFT) that support the results of the MESP study. The saturated scaffold FLPs can be promising candidates to improve the efficiency of catalysts in many reactions.
中文翻译：
使用金刚烷衍生的氨基硼烷挫败路易斯对对 1-甲基吡咯的 – –H 键进行无金属催化活化和硼化：密度泛函理论研究
受挫路易斯对 (FLP) 化学已发展成为有机化学催化的新策略，并为合成各种感兴趣的化合物开辟了一个新的无金属有机催化领域。金刚烷作为分子支架，用于设计新的 FLP（两亲分子）组，用于
使用 DFT (wB97XD/6-31 + G (d,p)) 理论水平的 –
H 活化和随后的 1-甲基吡咯硼化。饱和烃显示出以下能量学的改善 -
与用于此类反应的不饱和亚苯基 FLP 相比，1-甲基吡咯的 –H 活化和随后的硼化。金刚烷基衍生的 FLP 增强了路易斯酸和路易斯碱的特性，与相应的二聚体相比，负责催化活性的单体在能量上也更加稳定。在 1-NMe 2 -2-BH 2 -C 6 H 4 (I)和 1-Pip-2-BH 2 -C 6 的情况下，H 2挤出和亲电硼化步骤在吉布斯自由能表面上的能量相当H 4 (II) . 对于 1-NMe 2 -2-BH 2 -4-FC 10 H 13 (B)和 ~5.6 的金刚烷基支架 FLP，这些步骤激活的相对自由能垒已显着降低 ~5.5 和 ~3.7 kcal/mol 1-Pip-2-BH 2 -4-FC 10 H 13 (D) ~4.9 kcal/mol， 分别。金刚烷基 FLP 的增强反应性已通过分子静电势 (MESP) 研究得到合理化。使用支持 MESP 研究结果的概念密度泛函理论 (CDFT) 计算了路易斯碱和路易斯酸的亲核和亲电特征。饱和支架 FLP 可以成为提高催化剂在许多反应中效率的有希望的候选者。
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