A copper(I)-catalyzed diastereodivergent addition of phosphinothioates (HP(S)ROR') to alpha , beta -unsaturated thioamides is disclosed, which constructs vicinal P -chiral and C -chiral centers in generally high diastereoand enantioselectivities. In this reaction, the kinetic resolution of HP(S)ROR' occurs, which affords ( R )- HP(S)PhOMe in high enantioselectivity in the addition with ( R,R )-Ph-BPE as the ligand. It is found through control experiment that dual soft -soft interaction, indicated by both 1 H and 31 P NMR experiments, is indispensable in the present reaction. The first soft -soft interaction between copper(I) catalyst and HP(S)ROR' enables facile deprotonation to generate nucleophilic [Cu]-SPROR' species. The second one between the [Cu]-SPROR' species and alpha , beta -unsaturated thioamides facilitated the nucleophilic addition. Finally, both Michael adducts and ( R )-HP(S)PhOMe are easily converted to synthetically useful compounds. (c) 2024 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

The complete C-20 framework of brianthein W was established, featuring hydroboration/allylation, to provide the C1-C2 quaternary/tertiary stereoarray with excellent stereocontrol. Intramolecular nitrile oxide cycloaddition (INOC) was adopted as the key transformation to establish the trans-fused 6/10-bicyclic ring system. Evolution of the second INOC event revealed the intricacies governing regioselectivity, which ultimately led to construction of the highly strained 10-membered carbocycle.

An easily available chlorodifluoromethylating reagent YlideFluor-CF2Cl based on the sulfonium ylide skeleton was developed. Under blue light irradiation, YlideFluor-CF2Cl underwent homolytic S-C bond cleavage to generate ClCF2 center dot, which reacted with electron-rich alkenes or heteroarenes to afford the corresponding chlorodifluoromethylated products. Alternatively, YlideFluor-CF2Cl may act as an electrophilic chlorodifluoromethylating reagent to react directly with soft carbon nucleophiles derived from beta-ketoesters to give the chlorodifluoromethylated compounds in good yields.

Backbone planarity is an inherent structural feature for fused ring electron acceptors and one of important prerequisites for their high photovoltaic performance. However, for non-fused ring electron acceptors (NFREAs), it is a challenging task to achieve it. In this work, two NFREAs (Ph2TIC and BT2TIC) containing thiophenebenzene-thiophene or thiophene-benzothiadiazole-thiophene three non-fused aromatic rings in central scaffold were designed with an attempt to use a pair of 2,4,6-triisopropylphenyl substituents (referred as embracingtype side chains) at 3,3 '-positions of the two thiophene units to lock the backbone in a planar conformation. X-ray crystallography revealed that Ph2TIC has a quasi-planar backbone, whereas BT2TIC shows a twisted one, but both tend to form two-dimensional layered arrays through intermolecular 7C-7C stacking involving terminal acceptor moieties. UV-vis light-absorption spectroscopy showed that both compounds have similar optoelectronic properties either in dilute solutions or in solid film state, thus confirming the conformation-lock function of the embracing-type side chains. While for photophysical properties, BT2TIC displays a red-shifted broader light absorption spectrum as compared to Ph2TIC due to the introduction of an additional acceptor moiety in the structure. Ph2TIC and BT2TIC were evaluated as the acceptor materials in organic solar cells in combination with PM6, a typical donor polymer, and delivered the optimized power conversion efficiencies of 4.31 % and 3.78 %, respectively. Although the photovoltaic performances are modest, the work provides a new thought for maintaining the backbone planarity in NFREAs and would be useful in their future design.

Direct aerobic oxidation of silyl ethers to carboxylic acids has been developed. The mild reaction conditions lead to a broad range of functional group compatibility. Different types of silyl groups have been investigated and selective deprotective oxidation has been realized. The reaction could be conducted under air. Direct aerobic oxidation of silyl ethers to carboxylic acids using a series of mild reaction conditions has been developed.