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Divergent reactivity of nucleophilic 1-bora-7a-azaindenide anions†‡
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-12-12 00:00:00 , DOI: 10.1039/c7dt04350c Matthew M. Morgan 1, 2, 3, 4, 5 , J. Mikko Rautiainen 1, 6, 7, 8 , Warren E. Piers 1, 2, 3, 4, 5 , Heikki M. Tuononen 1, 6, 7, 8 , Chris Gendy 1, 2, 3, 4, 5
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-12-12 00:00:00 , DOI: 10.1039/c7dt04350c Matthew M. Morgan 1, 2, 3, 4, 5 , J. Mikko Rautiainen 1, 6, 7, 8 , Warren E. Piers 1, 2, 3, 4, 5 , Heikki M. Tuononen 1, 6, 7, 8 , Chris Gendy 1, 2, 3, 4, 5
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The reactions of 1-bora-7a-azaindenide anions, prepared in moderate to excellent yields by reduction of the appropriate 1-bora-7a-azaindenyl chlorides with KC8 in THF, with alkyl halides and carbon dioxide were studied. With alkyl halides (CH2Cl2, CH3I and BrCH(D)CH(D)tBu), the anions behave as boron anions, alkylating the boron centre via a classic SN2 mechanism. This was established with DFT methods and via experiments utilizing the neo-hexyl stereoprobe BrCH(D)CH(D)tBu. These reactions were in part driven by a re-aromatization of the six membered pyridyl ring upon formation of the product. Conversely, in the reaction of the 1-bora-7a-azaindenide anions with CO2, a novel carboxylation of the C-2 carbon alpha to boron was observed. Computations indicated that while carboxylation of the boron centre was kinetically feasible, the products of B-carboxylation were not thermodynamically favored relative to the observed C-2 carboxylated species, which were formed preferably due to the generation of both C–C and B–O bonds. In these products, the pyridyl ring remains non-aromatic, in part accounting for the observed reversibility of carboxylation.
中文翻译：
亲核性1-bora-7a-氮杂茚化物阴离子的发散反应性† ‡
研究了通过在THF中用KC 8还原适当的1-bora-7a-氮杂茚基氯化物与烷基卤化物和二氧化碳反应，以中等至极好的收率制备的1-bora-7a-氮杂茚阴离子。对于烷基卤（CH 2 Cl 2，CH 3 I和BrCH（D）CH（D）t Bu），这些阴离子表现为硼阴离子，通过经典的S N 2机理使硼中心烷基化。这是通过DFT方法并通过利用新己基立体探针BrCH（D）CH（D）t的实验确定的卜 这些反应部分地由产物形成时六元吡啶基环的重新芳构化驱动。相反，在1-硼-7a-氮杂茚阴离子与CO 2的反应中，观察到了C-2碳α向硼的新型羧化。计算表明，虽然硼中心的羧化在动力学上是可行的，但相对于观察到的C-2羧化物种，B羧化的产物在热力学上并不有利，这优选地是由于C–C和B–O的产生债券。在这些产物中，吡啶基环保持为非芳香族的，部分原因是观察到的羧化可逆性。
更新日期：2017-12-12
中文翻译：
亲核性1-bora-7a-氮杂茚化物阴离子的发散反应性† ‡
研究了通过在THF中用KC 8还原适当的1-bora-7a-氮杂茚基氯化物与烷基卤化物和二氧化碳反应，以中等至极好的收率制备的1-bora-7a-氮杂茚阴离子。对于烷基卤（CH 2 Cl 2，CH 3 I和BrCH（D）CH（D）t Bu），这些阴离子表现为硼阴离子，通过经典的S N 2机理使硼中心烷基化。这是通过DFT方法并通过利用新己基立体探针BrCH（D）CH（D）t的实验确定的卜 这些反应部分地由产物形成时六元吡啶基环的重新芳构化驱动。相反，在1-硼-7a-氮杂茚阴离子与CO 2的反应中，观察到了C-2碳α向硼的新型羧化。计算表明，虽然硼中心的羧化在动力学上是可行的，但相对于观察到的C-2羧化物种，B羧化的产物在热力学上并不有利，这优选地是由于C–C和B–O的产生债券。在这些产物中，吡啶基环保持为非芳香族的，部分原因是观察到的羧化可逆性。
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