Catalytic Hydrofunctionalization Reactions of 1,3-Diynes

Metal-catalyzed hydrofunctionalization reactions of alkynes, i.e., the addition of Y–H units (Y = heteroatom or carbon) across the carbon–carbon triple bond, have attracted enormous attention for decades since they allow the straightforward and atom-economic access to a wide variety of functionalized olefins and, in its intramolecular version, to relevant heterocyclic and carbocyclic compounds. Despite conjugated 1,3-diynes being considered key building blocks in synthetic organic chemistry, this particular class of alkynes has been much less employed in hydrofunctionalization reactions when compared to terminal or internal monoynes. The presence of two C≡C bonds in conjugated 1,3-diynes adds to the classical regio- and stereocontrol issues associated with the alkyne hydrofunctionalization processes’ other problems, such as the possibility to undergo 1,2-, 3,4-, or 1,4-monoadditions as well as double addition reactions, thus increasing the number of potential products that can be formed. In this review article, metal-catalyzed hydrofunctionalization reactions of these challenging substrates are comprehensively discussed.

Electrophilic Iodination of Organic Compounds Using Elemental Iodine or Iodides: Recent Advances 2008–2021: Part I

The iodination of organic compounds is of great importance in synthetic organic chemistry. It opens comprehensive approaches for the synthesis of various biologically active compounds. The recent advances in iodination of organic compounds using elemental iodine or iodides, covering the last thirteen years, are the objective of the present review.

The Advent and Development of Organophotoredox Catalysis

In the last decade, photoredox catalysis has unlocked unprecedented reactivities in synthetic organic chemistry. Seminal advancements in the field have involved the use of well-studied metal complexes as photoredox catalysts...

Synthesis of Acridinones via Palladium-Catalyzed Reductive Annulation of 2-Nitrobenzaldehydes and Resorcinols

Catalytic conversion of biomass-derived feedstocks into functional molecules is of significance to synthetic organic chemistry. Herein, through a palladium-catalyzed reductive annulation reaction of resorcinols and 2-nitrobenzaldehydes, we present a new...

Fast and automated identification of reactions with low barriers using meta-MD simulations

We test our meta-molecular dynamics (MD) based approach for finding low-barrier (<30 kcal/mol) reactions (SciPost Chem. 2021, 1, 003) on uni- and bimolecular reactions extracted from the barrier dataset developed by Grambow et al. (Scientific Data 2020, 7, 137). For unimolecular reactions the meta-MD simulations identify 25 of the 26 products found by Grambow et al., while the subsequent semiempirical screening eliminates an additional four reactions due to at an overestimation of the reaction energies or estimated barrier heights relative to DFT. In addition, our approach identifies an additional 36 reactions not found by Grambow et al., 10 of which are <30 kcal/mol. For bimolecular reactions the meta-MD simulations identify 19 of the 20 reactions found by Grambow et al., while the subsequent semiempirical screening eliminates an additional reaction. In addition, we find 34 new low-barrier reactions. For bimolecular reactions we found that it is necessary to ”encourage” the reactants to go to previously undiscovered products, by including products found by other MD simulations when computing the biasing potential as well as decreasing the size of the molecular cavity in which the MD occurs, until a reaction is observed. We also show that our methodology can find the correct products for two reactions that are more representative of those encountered in synthetic organic chemistry. The meta-MD hyperparameters used in this study thus appears to be generally applicable to finding low-barrier reactions.