21:T41b,Despite the significant achievements in dearomatization and C-H functionalization of arenes, the arene ring-opening remains a largely unmet challenge and is underdeveloped due to the high bond dissociation energy and strong resonance stabilization energy inherent in aromatic compounds. Herein, we demonstrate a novel carbene assisted strategy for arene ring-opening. The understanding of the mechanism by our DFT calculations will stimulate wide application of bulk arene chemicals for the synthesis of value-added polyconjugated chain molecules. Various aryl azide derivatives now can be directly converted into valuable polyconjugated enynes, avoiding traditional synthesis including multistep unsaturated precursors, poor selectivity control, and subsequent transition-metal catalyzed cross-coupling reactions. The simple conditions required were demonstrated in the late-stage modification of complex molecules and fused ring compounds. This chemistry expands the horizons of carbene chemistry and provides a novel pathway for arene ring-opening.22:T448,Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of the carborane cage, they have low nucleophilicity and are reluctant to alkylate. Moreover, asymmetric synthesis of chiral carboranes is still in its infancy. Herein we have achieved the first catalytic asymmetric N-alkylation of o-carboranyl amine, providing general access to diverse secondary o-carboranyl amines with high efficiency and enantioselectivity under mild conditions. For the first time, asymmetric organocatalysis was introduced to carborane chemistry. Key to the success is the use of in situ generated (naphtho-)quinone methides as the alkylating reagents and suitable chiral acid catalysts. This protocol is also applicable to the asymmetric S-alkylation of 1-SH-o-C₂B₁₀H₁₁. Control experiments and kinetic studies provided important insights into the reaction mechanism, which likely involves rate-determining generation of the quinone methide followed by fast and enantio-determining nucleophilic addition.23:T614a,

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