Fan Zi-Heng, Kang Jia-Xin, Jia Sihan, Pan Qiao-Jing, Cao Lei, Chen Xi-Meng, Xu Cong-Qiao, Ma Yan-Na, Chen Xuenian
School of Chemistry and Chemical Engineering, Henan Key Laboratory of Boron Chemistry and Advanced Materials, Henan Normal University Xinxiang Henan 453007 China.
Department of Chemistry, Southern University of Science and Technology Shenzhen 518055 China.
Chem Sci. 2024 Jul 26;15(34):13923-9. doi: 10.1039/d4sc03109a.
There exists an interplay between borane and a Lewis base in their adducts. However, studies on these adducts so far have mainly focused on the different reactions of B-H bonds with limited attention given to the influence of borane on the chemistry of the Lewis base, except for BF and BAr. Herein, we have synthesized novel borane adducts with pyridine derivatives, Py·BH, in which the coordination of BH efficiently achieved the intra-molecular charge transfer. The strong B-N bond in these adducts resulted in the formation of stable dearomatic intermediates of pyridine derivatives, confirmed by H and B NMR spectroscopy, from which different reactions have transpired to realize C(sp)-H and C(sp)-H functionalization under mild conditions. The BH pyridine derivatives are stable and do not dissociate or decompose during the reaction process. The high stability of the B-N bond makes this method a good option for boron-containing drugs with potential for use in boron neutron capture therapy (BNCT).
硼烷与路易斯碱在它们的加合物中存在相互作用。然而，迄今为止对这些加合物的研究主要集中在B-H键的不同反应上，除了BF和BAr外，对硼烷对路易斯碱化学性质的影响关注有限。在此，我们合成了新型的硼烷与吡啶衍生物的加合物Py·BH，其中BH的配位有效地实现了分子内电荷转移。这些加合物中强的B-N键导致吡啶衍生物形成稳定的去芳香化中间体，通过H和B NMR光谱证实，由此发生了不同的反应，以在温和条件下实现C(sp)-H和C(sp)-H官能化。BH吡啶衍生物是稳定的，在反应过程中不会解离或分解。B-N键的高稳定性使得该方法成为用于硼中子俘获疗法（BNCT）的含硼药物的一个良好选择。
