The first highly Z- and enantioselective class of ring-opening/cross-metathesis reactions is presented. Transformations are promoted in the presence of <2 mol % of chiral stereogenic-at-Mo monoaryloxide complexes bearing an adamantylimido ligand that are prepared and used in situ. Reactions involve meso oxabicyclic substrates and afford the desired pyrans in 50-85% yield and up to >98:<2 enantiomer ratio. Importantly, the desired chiral pyrans thus obtained bear a Z olefin either exclusively (>98:<2 Z/E) or predominantly (>or=87:13 Z/E).

Highly Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C-S, N-S, O-S, S-S, and Se-S bond cleavage/functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular.

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis.

In the past decades, significant advances have been made on radical Smiles rearrangement. However, the eventually formed radical intermediates in these reactions are limited to the amidyl radical, ...

Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl-Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines.

The quest to find milder and more sustainable methods to generate highly reactive, carbon-centred intermediates has led to a resurgence of interest in radical chemistry. In particular, carboxylic acids are seen as attractive radical precursors due their availability, low cost, diversity, and sustainability. Moreover, the corresponding nucleophilic carbon-radical can be easily accessed through a favourable radical decarboxylation process, extruding CO2 as a traceless by-product. This review summarizes the recent progress on using carboxylic acids directly as convenient radical precursors for the formation of carbon-carbon bonds via the 1,4-radical conjugate addition (Giese) reaction.

Direct decarboxylative Giese reactions.

Silver-mediated reactions have recently emerged as a frontier area in organic chemistry. Indeed, the remarkable property of silver as a single-electron oxidant has led to its exploitment into the field of radical chemistry. The excellent reactivity and high selectivity exhibited by silver salts in the activation of different organic substrates place them among the most prominent reagents in free radical reactions. The present review aims to provide the readers with a critical overview of silver-based radical reactions, especially emphasizing the reactivity, selectivity and a detailed description of the reaction mechanism with particular attention to the role of Ag(I)-based catalysts/reactants. The selected examples have been classified according to the type of radicals generated, namely carbon-centered radicals and heteroatom (such as nitrogen, oxygen, phosphorus, sulfur)-centered radicals. The generation of such radicals as well as their application in synthetic processes including oxidation, addition, coupling, and radical cascades have been described in detail.

Silver-Based Radical Reactions: Development and Insights

A silver-catalyzed decarboxylative addition/aryl migration/desulfonylation of N-phenyl-N-(phenylsulfonyl)methacrylamide with primary, secondary, and tertiary carboxylic acids was described. The protocol provides an efficient approach for the synthesis of α-all-carbon quaternary stereocenters amides and isoquinolinediones. It was proposed that the radical generated from the silver-catalyzed decarboxylation was involved in the sequence reaction.

Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids

An efficient Ag-catalyzed decarboxylative addition/aryl migration/desulfonylation reaction sequence is described to synthesize α-quarternary carboxylic amides.

Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids.

Selective C O bond formation: highly efficient radical dioxygenation of alkenes initiated by catalytic amount of tert -butyl hydroperoxide

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Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids

Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids.

Selective C O bond formation: highly efficient radical dioxygenation of alkenes initiated by catalytic amount of tert -butyl hydroperoxide