Department of Chemistry and Biochemistry, Center for Biomolecular Structure and Dynamics, University of Montana, Missoula, Montana 59812, United States.
Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, New Mexico 88003, United States.
J Am Chem Soc. 2023 Feb 1;145(4):2690-2697. doi: 10.1021/jacs.2c13199. Epub 2023 Jan 23.
Aliphatic alkylamines are abundant feedstock and versatile building blocks for many organic transformations. While remarkable progress has been made to construct C-N bonds on aliphatic and aromatic carbon centers, the activation and functionalization of C(sp)-NH bonds in primary alkylamines remain a challenging process. In the present work, we discovered an unprecedented method to directly activate the C(sp)-NH bond of primary alkylamines by a high-valent dinuclear Co(μ-O) diamond core complex. This reaction results in the installation of other functional groups such as halides and alkenes onto the α-carbon center concomitant with the 2-e oxidation of the nitrogen atom on the amino group to form NHOH. These results shed light on future development enabling versatile functionalization of primary alkylamines based on the dinuclear cobalt system. Moreover, our work suggests that a related high-valent copper-oxo intermediate is likely generated in the ammonia monooxygenase catalytic cycle to affect the oxidation of NH to NHOH.
脂肪族烷基胺是许多有机转化中丰富的原料和多功能构建块。虽然在构建脂肪族和芳香族碳中心上的 C-N 键方面已经取得了显著的进展，但对伯烷基胺中 C(sp)-NH 键的活化和功能化仍然是一个具有挑战性的过程。在本工作中，我们发现了一种前所未有的方法，通过高价双核 Co(μ-O) 金刚石核配合物直接活化伯烷基胺的 C(sp)-NH 键。该反应导致其他官能团（如卤素和烯烃）被安装到α-碳原子中心，同时氨基上的氮原子被 2e 氧化形成 NHOH。这些结果为未来的发展提供了启示，使基于双核钴体系的伯烷基胺能够进行多功能化。此外，我们的工作表明，在氨单加氧酶催化循环中可能生成了相关的高价铜-氧中间体，以影响 NH 向 NHOH 的氧化。
