Sergio Fernandez

Molecular dihydridoaluminates are widely used as hydride donors, yet their controlled conversion into low-valent aluminium metalloligands remains unexplored. Here we show that a dipyrromethene–diphosphine dihydridoaluminate acts as a masked aluminyl ligand upon reaction with group 10 metal precursors, undergoing dehydrogenation with H ₂ release, and affording well-defined Al(I)–M(II) complexes. In contrast, Ni(0) precursors undergo partial dehydrogenation via LiH extrusion to give hydridobridged Al–Ni aggregates, revealing an oxidation-state dependence. These findings establish dihydridoaluminates as versatile precursors to low-valent Al metalloligands and provide a platform for developing unique heterobimetallic systems.

Low‐valent pnictogen systems have recently emerged as redox catalysts for C–F activation. However, catalytic turnover has remained largely restricted to hydrodefluorination pathways reliant on metallomimetic reductive elimination. Herein, we report a defluorinative functionalization platform mediated by zwitterionic pnictinidenes that enables the formation of diverse C–X bonds (X = C, O, S, N, P, Se) from polyfluoro(hetero)arenes under mild conditions. Combined experimental and DFT studies reveal that, although a Sb(I)/Sb(III) redox cycle could be accessed, catalysis instead proceeds through Sb(III)–F species that promote C–F substitution via a redox‐neutral manifold. These findings establish catalyst speciation as a decisive mechanistic branch point, showing how strategies to modulate ligand scrambling events may enable alternative pnictogen‐based redox or redox‐neutral manifolds.

Low‐valent pnictogen systems have recently emerged as redox catalysts for C–F activation. However, catalytic turnover has remained largely restricted to hydrodefluorination pathways reliant on metallomimetic reductive elimination. Herein, we report a defluorinative functionalization platform mediated by zwitterionic pnictinidenes that enables the formation of diverse C–X bonds (X = C, O, S, N, P, Se) from polyfluoro(hetero)arenes under mild conditions. Combined experimental and DFT studies reveal that, although a Sb(I)/Sb(III) redox cycle could be accessed, catalysis instead proceeds through Sb(III)–F species that promote C–F substitution via a redox‐neutral manifold. These findings establish catalyst speciation as a decisive mechanistic branch point, showing how strategies to modulate ligand scrambling events may enable alternative pnictogen‐based redox or redox‐neutral manifolds.

Functionalization of fluorocarbons represents a central challenge in synthetic chemistry due to the exceptional strength of C–F bonds and the persistence of such compounds in the environment. Herein, we report the catalytic defluorinative functionalization of polyfluoro(hetero)arenes mediated by zwitterionic Sb and Bi species. These bis(NHC)borate-stabilized complexes enable C–X bond formation (X = C, O, S, N, P, Se) under mild conditions and a broad substrate scope. Mechanistic investigations, supported by DFT, reveal a dual landscape of redox and redox-neutral pathways, underscoring the metallomimetic behaviour of pnictinidenes in oxidative addition and highlighting the catalytic potential of pnictogen fluoride species. This work establishes zwitterionic Sb and Bi complexes as versatile catalysts for C–F bond activation, providing a general platform for main-group catalysis in defluorofunctionalization chemistry.

Herein, we describe a new class of zwitterionic heavier pnictogen species with bis ( N ‐heterocyclic carbene)borate as ligands, enabling the isolation of stable Sb and Bi species in multiple oxidation states. Computational analysis of zwitterionic pnictinidenes revealed their cationic character at the metal centre while holding unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in oxidative addition and reductive elimination processes, and display redox catalytic activity in hydrodefluorination reactions, marking a unique example of cationic pnictinidene catalysing a redox transformation and providing reactivity beyond the constraints of pincer ligands. Additionally, we report on a novel dehydrogenative thiolation of silanes. This work expands the scope of low‐valent pnictogen chemistry, providing a novel platform for main group redox catalysis.

Herein, we describe a new class of zwitterionic heavier pnictogen species with bis ( N ‐heterocyclic carbene)borate as ligands, enabling the isolation of stable Sb and Bi species in multiple oxidation states. Computational analysis of zwitterionic pnictinidenes revealed their cationic character at the metal centre while holding unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in oxidative addition and reductive elimination processes, and display redox catalytic activity in hydrodefluorination reactions, marking a unique example of cationic pnictinidene catalysing a redox transformation and providing reactivity beyond the constraints of pincer ligands. Additionally, we report on a novel dehydrogenative thiolation of silanes. This work expands the scope of low‐valent pnictogen chemistry, providing a novel platform for main group redox catalysis.

Herein we describe a new class of zwitterionic heavier pnictogen species with bis(NHC)borate as stabilizing ligands, enabling the isolation of Sb and Bi species in +1, +2, and +3 oxidation states. Computational analysis of zwitterionic pnictinidines revealed their cationis character, as well as unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in key organometallic transformations, including oxidative addition and reductive elimination pro-cesses, and display redox catalytic activity in hydrodefluorination reactions, marking a rare example of pnictinidine-catalyzed redox transformation beyond the constraints of pincer ligands. Additionally, we report on a novel dehydrogenative thiolation of silanes. This work expands the scope of low-valent pnictogen chemistry, providing a novel platform for main group redox catalysis.

Transition metal catalysis has contributed to the discovery of novel methodologies and the preparation of natural products, as well as new chances to increase the chemical space in drug discovery programs. In the case of marine drugs, this strategy has been used to achieve selective, sustainable and efficient transformations, which cannot be obtained otherwise. In this perspective, we aim to showcase how a variety of transition metals have provided fruitful couplings in a wide variety of marine drug-like scaffolds over the past few years, by accelerating the production of these valuable molecules.

Indole is a versatile pharmacophore widely distributed in bioactive natural products. This privileged scaffold has been found in a variety of molecules isolated from marine organisms such as algae and sponges. Among these, indole alkaloids represent one of the biggest, most promising family of compounds, having shown a wide range of pharmacological properties including anti-inflammatory, antiviral, and anticancer activities. The aim of this review is to show the current scenario of marine indole alkaloid derivatives, covering not only the most common chemical structures but also their promising therapeutic applications as well as the new general synthetic routes developed during the last years.

Indole is a versatile pharmacophore widely distributed in bioactive natural products. This privileged scaffold has been found in a variety of molecules isolated from marine organisms such as algae and sponges. Among these, indole alkaloids represent one of the biggest, most promising family of compounds, having shown a wide range of pharmacological properties, including anti-inflammatory, antiviral and anticancer activities. The aim of this review is to show the current scenario of marine indole alkaloid derivatives, covering not only the most common chemical structures, but also new synthetic routes developed during the last years as well as promising therapeutic applications.