Herein, we established a copper-catalyzed asymmetric alkynylation of the sp 2 C-H bond of silylallenes, which was presented as an efficient method for the synthesis of enantioenriched skipped diynes with excellent enantioselectivity. The reaction was initiated by hydrogen atom abstraction of sp 2 allenic C-H bonds, in which the resonance forms of allenic and propargylic radicals were chemo- and enantioselectively trapped by chiral alkynyl-Cu(II) species to deliver a variety of skipped diynes. The method features a broad substrate scope and robust functional group tolerance, accommodating both alkynyl silanes and boronic esters. Moreover, the resulting skipped diynes serve as versatile key synthons for incorporating enantiomerically enriched enynes, alkynes, alkanes, and their derivatives, which could be applied in the concise synthesis of several bioactive molecules.

Stress granules (SGs) are stress-induced membraneless organelles whose dynamics are tightly regulated by protein interactions and modifications. However, whether SUMOylation directly targets SG core proteins G3BP1/2 and which ligase is involved remains unclear, partly due to their transient and membraneless nature. To investigate this SUMOylation and its ligase, we applied our low-concentration formaldehyde crosslinking (lcFAX) method to stabilize SGs and enhance analysis. Using lcFAX-MS, we identified TRIM28 as a previously undefined SG-associated protein and showed that it SUMOylates G3BP1 at K287 and G3BP2 at K281, establishing a critical mechanism regulating SG dynamics that ultimately impacts cellular ROS and apoptosis. In addition, lcFAX-seq provides insights into SG RNA composition. Altogether, our study uncovers an essential role for TRIM28-mediated SUMOylation in modulating SG dynamics. TRIM28 may act as aversatile regulator, and with the aid of lcFAX, this mechanism could be further explored across diverse membraneless organelles and regulatory pathways.

A method is described for the synthesis of alpha-aryl and allylic sulfones and sulfonamides through CuBr/oxalamide-catalyzed coupling at 40 degrees C. This transformation involves coupling with (hetero)aryl or vinyl bromides and 2-substituted sulfonylacetates (or amide analogues), proceeding via spontaneous hydrolysis and decarboxylation. The conditions are compatible with various functional groups and heterocycles, allowing for the diverse syntheses of the target compounds.

A gold-catalyzed cascade cyclization of ene-ynamides bearing a propargyl carboxylate moiety has been developed, which involves a 1,2-migration of the alkene substituent as a key step. The method provides an efficient route for the synthesis of functionalized 2-acylquinolines, with high selectivity favoring 1,2-aryl migration over 1,2-H or -alkyl migration. In addition, the nature of the propargylic substituent has a significant effect on the reaction outcome. When an aryl substituent is present, 2-indenyl-substituted indole is formed via a cyclopropyl gold carbene intermediate, leading to cleavage of the C=C bond in the ene-ynamide substrate.

Constructing new Bronsted acid sites within zeolitic materials holds paramount importance for the advancement of solid-acid catalysis. Zeo-type germanosilicates, a class of metallosilicates with a neutral framework composed of tetravalent Ge and Si oxygen tetrahedrons, are conventionally considered not to generate Bronsted acid sites. Herein, we disclose an abnormal phenomenon with Ge-rich IWW-type germanosilicate (IWW-A) as an example that Ge-enriched germanosilicates are featured by mild Bronsted acidity. Using the art-of-state density functional theory calculation, 19F magic angle spinning nuclear magnetic resonance, microcalorimetric and ammonia infrared mass spectrometry- temperature-programmed desorption characterizations, the nature of germanosilicate's Bronsted acidity has been demonstrated to be closely related to the neighboring framework Ge-hydroxyl pairs. Besides, the contribution of Ge-OH groups to Bronsted acidity and the role of Ge-pair structure for maintaining mild acid strength have been elucidated. In catalytic cracking of n-hexane and methanol-to-olefins reaction, the IWW-A germanosilicate exhibit high light olefins selectivity, good recyclability and low carbon deposition, outperforming the benchmark zeolite catalyst, ZSM-5 aluminosilicate. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.