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Frontiers in Halogen and Chalcogen-Bond Donor DOI: 10.1002/cctc.201901215 Minireviews 1 2 3 Frontiers in Halogen and Chalcogen-Bond Donor 4 5 Organocatalysis 6 [a] [a] [a] 7 Julia Bamberger, Florian Ostler, and Olga García Mancheño* 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 ChemCatChem 2019, 11, 1–15 1 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim These are not the final page numbers! �� Wiley VCH Mittwoch, 21.08.2019 1999 / 145245 [S. 1/15] 1 Minireviews 1 Non-covalent molecular interactions on the basis of halogen Being particularly relevant in the binding of “soft” substrates, 2 and chalcogen bonding represent a promising, powerful the similar strength to hydrogen bonding interactions and its 3 catalytic activation mode. However, these “unusual” non- higher directionality allows for solution-phase applications with 4 covalent interactions are typically employed in the solid state halogen and chalcogen bonding as the key interaction. In this 5 and scarcely exploited in catalysis. In recent years, an increased mini-review, the special features, state-of-the-art and key 6 interest in halogen and chalcogen bonding have been awaken, examples of these so-called σ-hole interactions in the field of 7 as they provide profound characteristics that make them an organocatalysis are presented. 8 appealing alternative to the well-explored hydrogen bonding. 9 10 1. Introduction including crystal engineering,[8] supramolecular[9] and medicinal 11 chemistry.[8a,10] Besides the correlation to the electrostatic 12 To achieve an effective catalytic transformation, the structural potential, also charge transfer and dispersion is believed to give 13 design of selective catalyst structures requires the correct rise to σ-hole interactions.[11] Associated with σ* orbitals, the σ- 14 manipulation of the energetic and stereochemical features of hole deepens with heavier atoms (going from the top to the 15 intermolecular forces. Although metal-free organocatalysis has bottom of the periodic table) and with a higher polarizability, 16 existed for more than a century,[1] only recently a tremendous which increases from right to left in the periodic table.[12] Due to 17 interest in this area aroused, due to the many opportunities the existence of a second substituent, it appears that chalcogen 18 that organocatalytic systems may offer in terms of catalyst atoms possess two σ-holes,[13] whereas one σ-hole is available 19 design. Thus, many organocatalytic systems rely on the for a halogen atom (Figure 1a).[8a] 20 cooperation of multiple non-covalent interactions, including a Furthermore, electron-withdrawing residues geminal to the 21 large range of attractive and repulsive forces.[2] Amongst others, X or Ch atom, respectively, increase the σ-hole(s) and allow for 22 the main interactions include ion-pairing, ion-dipole interac- the formation of strong X and Ch complexes.[8a,15] Besides their 23 tions, dipole-dipole interactions and hydrogen bonding. Many classification as soft Lewis acids, which plays an important role 24 powerful organocatalysts have been designed on the basis of in substrate preference, halogen and chalcogen bonds are 25 the latter, as its strength and directionality opens new significantly more directional than hydrogen bonding interac- 26 possibilities to access more complex molecular targets.[3] tions. This aspect is particularly important for a strong complex- 27 However, in terms of the “hard and soft (Lewis) acids and bases” ation and requires angles close to 180° for RÀ Ch/X···LB (Lewis 28 (HSAB) concept,[4] catalysts derived from hydrogen bonding base).[16] This is attributed to two specific characteristics: a) the 29 share one certain disadvantage. As the substrate activation σ* interactions of the RÀ H bond occur via a 1 s orbital and b) 30 relies on the interaction through the “hard” hydrogen atom,[5] the lack of filled p-orbitals on the valency of the latter.[13c] 31 “soft” starting materials may be only weakly coordinated or Regarding halogen and chalcogen bonding, most of their 32 completely disregarded. Even though a vast amount of work on applications concern the solid state, whereas their employment 33 hydrogen bonding catalysis has paved the way to readily in solution has largely lagged behind. However, taking into 34 understand the underlying mechanisms and allowed for the account the similarities to hydrogen bonding, the application of 35 development of highly asymmetric transformations,[1,3b,6] the halogen and chalcogen bonding in solution was a logical 36 strong focus on one interacting atom does not allow for much consequence. In general, the Xs and Chs are able to bind more 37 variation towards orbital sizes and polarizabilities. In light of strongly to the substrate and can thereby create more rigid 38 this, halogen (X) and chalcogen (Ch) bonding have emerged as preorganized structures, which is likely to be beneficial to the 39 promising alternatives and have been introduced as a key stabilization of catalytic intermediates. However, the strict 40 interaction for the design of novel organocatalysts. While their geometric requirements make it extremely challenging for 41 direct origin is still under debate, the so called σ-hole both, the design and the synthesis of X-bond- and Ch-bond- 42 interactions are originated from an anisotropically distributed 43 electron density along the RÀ X or the RÀ Ch bond. This results in 44 the appearance of frequent electropositive regions, which make 45 the X or the Ch atom adopt a Lewis acidic role. This region is 46 predestined to form non-covalent interactions with Lewis basic 47 compounds and is usually referred to as the σ-hole.[7] These 48 interactions have been observed in many different contexts, 49 50 51 [a] Dr. J. Bamberger, F. Ostler, Prof. O. G. Mancheño 52 Organic Chemistry Institute Münster University 53 Corrensstraße 40 54 Münster D-48149 (Germany) 55 E-mail: [email protected] This manuscript is part of the Special Issue on New Concepts in Homo- Figure 1. a) σ-Holes that are predicted to increase with heavier atoms and a 56 [14] geneous Catalysis. higher polarizability. b) Model structures candidates explored in catalysis. 57 ChemCatChem 2019, 11, 1–15 www.chemcatchem.org 2 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim These are not the final page numbers! �� Wiley VCH Mittwoch, 21.08.2019 1999 / 145245 [S. 2/15] 1 Minireviews based catalysts. Nevertheless, non-covalent halogen and chalc- 1 ogen bonding in solution have only recently been applied in 2 organocatalysis. While the use of halogen[8a,9b,17] and 3 chalcogen[13,18] bonding has been reviewed in several articles 4 from different perspectives, we wish to provide herein an 5 introductory overview of halogen and chalcogen bonding and 6 their way into non-covalent organocatalysis. Consequently, in 7 this minireview only organocatalytic activation modes of XB- 8 donor and ChB-donor catalysis will be discussed. Thus, catalysis 9 by elemental halides or chalcogens, as well as transient and XB- 10 or ChB-assisted catalysis will not be covered. 11 12 Scheme 1. Pioneer XB-bond catalyzed reduction of quinolines by Bolm et al. 13 2. Halogen Bonding 14 15 In the last years, the research field of halogen-bonding (XB) is 16 gaining increasing attention in the field of organocatalysis. catalytic methods often require harsh conditions, which might 17 Generally speaking, the ability of a halogen-bond-donor (XB- enable unwanted side reactions to occur, or need a stoichio- 18 donor) to establish a halogen bond strongly depends on the metric amount of a Lewis acid. Therefore, catalytic Lewis acids 19 polarizability of the XB-donor atom (I>Br>Cl@F), as well as on are of great interest and have been explored on a broad scope. 20 the electronic properties of the attached residue on the halogen Along with the aforementioned HB-donors, XB-donors have 21 atom.[8a] As a consequence, most of the reported structures in recently also found application in this field and are promising 22 XB-donor catalysis rely on the higher polarized iodine-based candidates to overcome challenging disadvantages of their HB- 23 derivatives. Moreover, in analogy to the more explored hydro- donor analogues, due to their higher directionality and usually 24 gen-bond catalysis, typical benchmark and test reactions for XB- stronger binding affinities. 25 donors often involve the activation of neutral substrates such as 26 carbonyls (aldehydes, ketones or imines) or heteroarenes (e.g. 27 quinolines), and more recently halide-abstraction reactions 2.1.1. N-Heteroarene Reduction Reactions 28 involving an anion-binding-type activation. Therefore, this 29 section is divided according to these two main activation Most probably, the first organocatalytic reaction employing XB- 30 approaches. Thus, the pioneer and the most recent examples of donors was reported in 2008 by Bolm and coworkers.[19] In this 31 this type of activation in organocatalysis is presented. work, the reduction of quinolines using haloperfluoroalkanes 1 32 in the presence of Hantzsch ester was achieved, in which the 33 activation of the quinoline by halogen bonding was crucial 34 2.1. Catalytic Activation of Neutral Substrates (Scheme 1). 35 In 2014, the group of Tan followed this approach and 36 The catalytic activation of neutral electrophiles, such as ketones, carried out some attempts towards an asymmetric reduction of 37 aldehydes or imines are of high synthetic significance as non- quinolines by employing bidentate dihydroimidazolines of type 38 39 40 Julia Bamberger, born in 1990, studied Olga García Mancheño received her PhD in 41 chemistry at the University of Regensburg and 2005 from the Universidad Autónoma de 42 obtained her M.Sc.
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