Hydroamination, Aminoboration, and Carboamination with Electrophilic Amination Reagents: Umpolung-Enabled Regio- and Stereoselective Synthesis of N-Containing Molecules from Alkenes and Alkynes

Nitrogen (N) is ubiquitously found in bioactive molecules, pharmaceutical agents, and organic functional materials. Accordingly, development of new C–N bond-forming catalysis has been one of the long-standing research subjects in synthetic organic chemistry. In this Perspective, recent advances in highly selective amination reactions with electrophilic amination reagents are described: by taking advantage of the concept of nitrogen umpolung, otherwise challenging aminofunctionalizations, such as hydroamination, aminoboration, and carboamination, of readily available feedstock-like alkenes and alkynes are possible, giving densely functionalized complex and often chiral alkylamines with high selectivity. The scope, limitations, and reaction mechanism are briefly summarized.Hirano K., Miura M.. Hydroamination, Aminoboration, and Carboamination with Electrophilic Amination Reagents: Umpolung-Enabled Regio- and Stereoselective Synthesis of N-Containing Molecules from Alkenes and Alkynes. Journal of the American Chemical Society. 144(2), 648-661, (2022), 19 January 2022; © 2022 American Chemical Society. https://doi.org/10.1021/jacs.1c12663

Stripe antiferromagnetic correlations in LaFeAsO1-xFx probed by 75As NMR

The anisotropy of the nuclear spin-lattice relaxation rate $1/T_{1}$ of $^{75}$As was investigated in the iron-based superconductor LaFeAs(O$_{1-x}$F$_{x}$) ($x = 0.07, 0.11$ and 0.14) as well as LaFeAsO. While the temperature dependence of the normal-state $1/T_1T$ in the superconducting (SC) $x = 0.07$ is different from that in the SC $x = 0.11$, their anisotropy of $1/T_1$, $R \equiv (1/T_{1})_{H \parallel ab}/(1/T_{1})_{H \parallel c}$ in the normal state is almost the same ($\simeq$ 1.5). The observed anisotropy is ascribable to the presence of the local stripe correlations with $Q = (\pi, 0)$ or $(0, \pi)$. In contrast, $1/T_1$ is isotropic and $R$ is approximately 1 in the overdoped $x = 0.14$ sample, where superconductivity is almost suppressed. These results suggest that the presence of the local stripe correlations originating from the nesting between hole and electron Fermi surfaces is linked to high-$T_c$ superconductivity in iron pnictides.Comment: 4 pages, 3 figures, Accepted for publication in Phys. Rev.