Potter Tyler J, Kamber David N, Mercado Brandon Q, Ellman Jonathan A
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
ACS Catal. 2017 Jan 6;7(1):150-153. doi: 10.1021/acscatal.6b03217. Epub 2016 Dec 2.
The transition metal catalyzed C-H bond addition to nitroalkenes has been developed. Very broad nitroalkene scope was observed for this Rh(III)-catalyzed method, including for aliphatic, aromatic and β,β-disubstituted derivatives. Additionally, various directing groups and both aromatic and alkenyl C-H bonds were effective in this transformation. Representative nitroalkane products were converted to dihydroisoquinolones and dihydropyridones in a single step and in high yield by iron mediated reduction and cyclization. Moreover, preliminary success in enantioselective Rh(III)-catalyzed C-H bond addition to nitroalkenes was achieved as was X-ray structural characterization of a nitronate intermediate.
已经开发出过渡金属催化的碳氢键加成到硝基烯烃的反应。对于这种铑(III)催化的方法,观察到硝基烯烃的适用范围非常广泛,包括脂肪族、芳香族和β,β-二取代衍生物。此外,各种导向基团以及芳香族和烯基碳氢键在这种转化中都是有效的。具有代表性的硝基烷烃产物通过铁介导的还原和环化反应,一步高产率地转化为二氢异喹啉酮和二氢吡啶酮。此外,在对映选择性铑(III)催化的碳氢键加成到硝基烯烃的反应中取得了初步成功,并且获得了硝酮中间体的X射线结构表征。