†Department of Chemistry, Boston College, Chestnut Hill, Massachusetts 02467-3860, United States.
‡Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403-1253, United States.
J Am Chem Soc. 2015 Apr 29;137(16):5536-41. doi: 10.1021/jacs.5b01916. Epub 2015 Apr 20.
The first general late-stage functionalization of monocyclic 1,2-azaborines at the C(6) position is described. Ir-catalyzed C-H borylation occurs regioselectively at the C(6) position of B-substituted 1,2-azaborines and is compatible with a range of substitution patterns at boron (e.g., hydride, alkoxide, alkyl, and aryl substituents). Subsequent Suzuki cross coupling with aryl- and heteroaryl bromides furnishes 1,2-azaborine-based biaryl compounds including 6-[pyrid-2-yl]-1,2-azaborines that represent novel κ(2)-N,N-bidentate ligands. The 6-[pyrid-2-yl]-B-Me-1,2-azaborine ligand has been demonstrated to form an emissive coordination complex with dimesitylboron that exhibits bathochromically shifted absorption and emission maxima and a higher photoluminescence quantum yield compared to its carbonaceous analogue.
首次对单环 1,2-氮杂硼烷在 C(6)位进行了一般性的晚期功能化。铱催化的 C-H 硼化反应在 B 取代的 1,2-氮杂硼烷的 C(6)位上具有区域选择性，并且与硼上的各种取代模式（例如氢化物、烷氧基、烷基和芳基取代基）相容。随后与芳基和杂芳基溴进行 Suzuki 交叉偶联，可得到基于 1,2-氮杂硼烷的联芳基化合物，包括 6-[吡啶-2-基]-1,2-氮杂硼烷，它们代表新型的 κ(2)-N,N-双齿配体。已经证明，6-[吡啶-2-基]-B-Me-1,2-氮杂硼烷配体可与二甲基硼形成发光配位络合物，与碳类似物相比，其吸收和发射最大值发生红移，并且光致发光量子产率更高。
