Journal ArticleDOI
Iodine(III) Derivatives as Halogen Bonding Organocatalysts
TLDR
First strong indications for the crucial role of halogen bonding in this kind of catalyses are presented, including the solvolysis of benzhydryl chloride and the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone.Abstract:
Hypervalent iodine(III) derivatives are known as versatile reagents in organic synthesis, but there is only one previous report on their use as Lewis acidic organocatalysts. Herein, we present first strong indications for the crucial role of halogen bonding in this kind of catalyses. To this end, the solvolysis of benzhydryl chloride and the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone served as benchmark reactions for halide abstraction and the activation of neutral compounds. Iodolium compounds (cyclic diaryl iodonium species) were used as activators or catalysts, and we were able to markedly reduce or completely switch off their activity by sterically blocking one or two of their electrophilic axes. Compared with previously established bidentate cationic halogen bond donors, the monodentate organoiodine derivatives used herein are at least similarly active (in the Diels-Alder reaction) or even decidedly more active (in benzhydryl chloride solvolysis).read more
Citations
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Journal ArticleDOI
Catalysis of Organic Reactions through Halogen Bonding
TL;DR: Halogen bonding, the noncovalent interaction based on electrophilic halogen substituents, features very interesting properties, as illustrated by numerous applications continuously emerging in this paper.
Journal ArticleDOI
Frontiers in Halogen and Chalcogen‐Bond Donor Organocatalysis
TL;DR: In this mini‐review, the special features, state‐of‐the‐art and key examples of these so‐called σ‐hole interactions in the field of organocatalysis are presented.
Journal ArticleDOI
Chalcogen Bonding Catalysis of a Nitro-Michael Reaction.
TL;DR: The first application of dicationic tellurium‐based chalcogen bond donors in the nitro‐Michael reaction between trans‐β‐nitrostyrene and indoles constitutes the first activation of nitro derivatives by chalCogen bonding (and halogen bonding).
Journal ArticleDOI
Chiral Hypervalent Iodines: Active Players in Asymmetric Synthesis.
TL;DR: The intention of the present review is to highlight as a whole the many approaches utilized up to date to prepare chiral iodines(III/V), as well as their reactivity in a comprehensive manner.
Journal ArticleDOI
Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes
TL;DR: The mechanism of the aryl iodide-catalyzed asymmetric migratory geminal difluorination of β-substituted styrenes has been explored with density functional theory computations and multiple attractive non-covalent interactions are found to underlie the high asymmetric induction.
References
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Journal ArticleDOI
The Halogen Bond
Gabriella Cavallo,Pierangelo Metrangolo,Pierangelo Metrangolo,Roberto Milani,Tullio Pilati,Arri Priimagi,Giuseppe Resnati,Giancarlo Terraneo +7 more
TL;DR: The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.
Journal ArticleDOI
Chemistry of Polyvalent Iodine
TL;DR: The present review summarizes the data that appeared in the literature following publication of previous reviews in 1996 and 2002 and is organized according to the classes of organic polyvalent iodine compounds with emphasis on their synthetic application.
Journal ArticleDOI
Definition of the halogen bond (IUPAC Recommendations 2013)
Gautam R. Desiraju,P. Shing Ho,Lars Kloo,Anthony C. Legon,Roberto Marquardt,Pierangelo Metrangolo,Peter Politzer,Giuseppe Resnati,Kari Rissanen +8 more
TL;DR: In this article, a definition for the term ''halogen bond'' is proposed, which designates a specific subset of the inter-and intramolecular interactions involving a halogen atom in a molecular entity.
Journal ArticleDOI
Advances in Synthetic Applications of Hypervalent Iodine Compounds
TL;DR: One of the goals of this Review is to attract the attention of the scientific community as to the benefits of using hypervalent iodine compounds as an environmentally sustainable alternative to heavy metals.