Blue light-induced diazo cross-coupling: synthesis of allyldiazo compounds through reshuffling of functionalities.

In this paper, we describe a new type of cross-coupling between simple diazo and vinyldiazo compounds that gives access to unusual allyldiazo products. Blue light discriminates two diazo compounds towards free carbene formation, triggering sequential cyclopropenation, (3+2) cycloaddition and ring opening rearrangement processes. This strategy involves an overall reshuffle of diazo functionality and olefinic carbons of vinyldiazo compounds with an extrusion of nitrogen.

Single-Cell Informatics for Tumor Microenvironment and Immunotherapy.

Cancer comprises malignant cells surrounded by the tumor microenvironment (TME), a dynamic ecosystem composed of heterogeneous cell populations that exert unique influences on tumor development. The immune community within the TME plays a substantial role in tumorigenesis and tumor evolution. The innate and adaptive immune cells "talk" to the tumor through ligand-receptor interactions and signaling molecules, forming a complex communication network to influence the cellular and molecular basis of cancer.

Understanding the Tumor Microenvironment in Melanoma Patients with In-Transit Metastases and Its Impacts on Immune Checkpoint Immunotherapy Responses.

Melanoma is the leading cause of global skin cancer-related death and currently ranks as the third most commonly diagnosed cancer in Australia. Melanoma patients with in-transit metastases (ITM), a type of locoregional metastasis located close to the primary tumor site, exhibit a high likelihood of further disease progression and poor survival outcomes. Immunotherapies, particularly immune checkpoint inhibitors (ICI), have demonstrated remarkable efficacy in ITM patients with reduced occurrence of further metastases and prolonged survival.

Photoredox radical/polar crossover enables C-H -difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes.

A photocatalytic C-H -difunctionalization of 1,3-benzodioxoles with two different alkenes for the synthesis of highly functionalized monofluorocyclohexenes is described. Using 4CzIPN as the photocatalyst, the direct single electron oxidation of 1,3-benzodioxoles allows their defluorinative coupling with α-trifluoromethyl alkenes to produce -difluoroalkenes in a redox-neutral radical polar crossover manifold. The C-H bond of the resultant γ,γ-difluoroallylated 1,3-benzodioxoles was further functionalized radical addition to electron-deficient alkenes using a more oxidizing iridium photocatalyst.