Iron-catalyzed C-7 selective NH2 amination of indoles.

7-Aminoindoles are important synthetic intermediates to a broad range of bioactive molecules. Transition metal-catalyzed directed C-H amination is among the most straightforward route for their synthesis, whereas methods that could directly incorporate an NH2 group in a highly selective manner remains elusive. Moreover, there is still high demand for the development of earth-abundant metal catalysis for such attractive reactivity. We present here the first C-7 selective NH2 amination of indoles through a directed homolytic aromatic substitution (HAS) with iron-aminyl radical. The reaction exhibits broad substrate scope, tolerates variety of functional groups, and is readily scalable with catalyst loading down to 0.1 mol% and turnover number (TON) up to 4500.

Hydroamination of Unactivated Alkenes with Aliphatic Azides.

We report here an efficient and highly diastereoselective intermolecular anti-Markovnikov hydroamination of unactivated alkenes with aliphatic azides in the presence of silane. The system tolerates a wide range of azides and alkenes and operates with alkene as limiting reagent. Mechanistic studies suggest a radical chain pathway that involves aminium radical formation, radical addition to alkenes and HAT from silane to ß-aminium alkyl radical. The use of sterically bulky silane is proposed to contribute to the excellent diastereoselectivity for HAT. Computational analysis uncovers the reaction pathway of aliphatic azide activation with silyl radical for aminyl radical formation.

[Effects of NaCl stress on Hippophae rhamnoides and Shepherdia argentea seedlings growth and photosynthetic characteristics].

With two-year old seedlings of Hippophea rhamnoides and Shepherdia argentea as test materials, this paper studied their growth and photosynthetic characteristics under the stress of different concentration (0, 200, 400 and 600 mmol x L(-1)) NaCl. The results showed that the biomass and total leaf area per plant of H. rhamnoides and S. argentea seedlings decreased significantly with increasing NaCl concentration. Comparing with the control, the root/shoot ratio of H. rhamnoides and S. argentea seedlings under NaCl stress increased obviously, while the leaf mass per area (LMA) decreased slightly. When the NaCl concentration increased and the stress time prolonged, the net photosynthetic rate (P(n)), transpiration rate (T(r)), and stomatal conductance (G(s)) of H. rhamnoides and S. argentea seedlings declined markedly, the intercellular CO2 concentration (C(i)) increased after an initial decrease, whereas the water use efficiency (WUE) and stomatal limiting value (L(s)) decreased after an initial increase. The dynamic changes of G(s), C(i) and L(s) indicated that the decline of P(n) was mainly caused by the stomatal limitation in a short-term stress, and by non-stomatal limitation in a long-term stress. The poorer the salt tolerance of tree species and the higher the NaCl concentration, the earlier the transition from stomatal limitation to non-stomatal limitation would occur. As for H. rhamnoides, its morphological symptoms of salt injury appeared on the 10th day, and all of its seedlings were died on the 22th day under 600 mmol NaCl x L(-1) stress. In contrast, S. argentea could tolerate 600 mmol NaCl x L(-1) stress for above 30 days, illustrating that S. argentea, as an introduced tree species, had higher salt tolerance than H. rhamnoides, and could be planted widely in saline regions of China.