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The enantioconvergent C(sp 3 )-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N -alkyl (hetero)aromatic amines yet has remained unexplored due to the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed enantioconvergent radical C(sp 3 )-N cross-coupling of activated racemic alkyl halides with (hetero)aromatic amines under ambient conditions. The key to success is the judicious selection of appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties for the formation of a stable and rigid chelating Cu complex. Thus, this kind of ligand could not only enhance the reducing capability of a copper catalyst to provide an enantioconvergent radical pathway but also avoid the coordination with other coordinating heteroatoms, thereby overcoming catalyst poisoning and/or chiral ligand displacement. This protocol covers a wide range of coupling partners (89 examples for activated racemic secondary/tertiary alkyl bromides/chlorides and (hetero)aromatic amines) with high functional group compatibility. When allied with follow-up transformations, it provides a highly flexible platform to access synthetically useful enantioenriched amine building blocks.

Due to the fascinating features, pulsating solitons attract much attention in the field of nonlinear soliton dynamics and ultrafast lasers. So far, most of the investigations on pulsating soliton are conducted in Er-doped fiber lasers. In this work, we reported the periodic transition between two evolving pulsating soliton states in an Yb-doped fiber laser. By using the real-time measurement techniques, the spectral and temporal characteristics of this transition state were investigated. Two evolving soliton pulsation states have similar evolution process, i.e., from pulsating towards quasi-stable mode-locked states. However, the details of the two processes are different, such as the pulse energy levels, pulsating modulation depths, duration of quasi-stable mode-locked states. The transition between two evolving soliton pulsation states could be attributed to the interaction of the polarizer and the varying polarization states of the pulse inside the laser cavity. The experimental results will contribute to the further understanding of soliton pulsating dynamics in dissipative optical systems.

It is highly desirable to avoid using rare or toxic metals for oxidative reactions in the synthesis of pharmaceuticals and fine chemicals. Hypervalent iodine compounds are environmentally benign alternatives, but their catalytic use has been quite limited. Herein, the protocol for in situ hypoiodite-catalyzed oxidative rearrangement of chalcones is first realized under mild and metal-free conditions, which provided a nontoxic, environmental-benign, and catalytic alternative to the thallium-based protocol. Also, the applicability and effectiveness of this catalytic protocol got well demonstrated via gram-scale synthesis and product derivatization. What is more, control and NMR tracking experiments were performed to figure out the possible catalytic species and intermediates.

Soliton pulsation is one of the most fascinating phenomena in ultrafast fiber lasers, owing to its rich nonlinear dynamics and potential generation of high peak power pulse. However, it is still a challenge to efficiently search for pulsating soliton in fiber lasers because it requires a fine setting of laser cavity parameters. Here, we report the autosetting soliton pulsation in a passively mode-locked fiber laser. The parameters of electronic polarization controller are intelligently adjusted to search for pulsating soliton state by the improved depth-first search algorithm. Moreover, the intensity modulation depth of pulsating soliton could be flexibly controlled. These findings indicate that the intelligent control of a fiber laser is an effective way to explore on-demand soliton dynamics and is also beneficial to the optimization of ultrafast laser performance.

We describe a photoinduced copper-catalyzed asymmetric radical decarboxylative alkynylation of bench-stable N-hydroxyphthalimide(NHP)-type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp 3 )-C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo- and cross-coupling catalyst but also tuning of the NHP-type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP-type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl-, allyl-, and aminocarbonyl-substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method., (© 2020 Wiley-VCH GmbH.)

A readily accessible and bench-stable water-soluble hypervalent iodine(III) reagent ( phenyl iodonio) sulfam ate (PISA) with an I-N bond was synthesized, and its structure was characterized by X-ray crystallography. With PISA, various indoles were synthesized via C-H amination of 2-alkenylanilines involving an aryl migration/intramolecular cyclization cascade with excellent regioselectivity in aqueous CH 3 CN. Notably, using this new method as the key step, not only two drug molecules, indometacin and zidometacin, but also another bioactive molecule, pravadoline, were synthesized.