Organocatalysis by a multidentate halogen-bond donor: an alternative to hydrogen-bond based catalysis

Perera, Manomi D.; Aakeröy, Christer B.

doi:10.1039/c9nj01404g

Cited by 26 publications

(31 citation statements)

References 25 publications

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“…Similarly to their closely related H-bond cousin, this class of bonds [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25] are derived from a primary electrostatic attraction, supplemented by substantial amounts of charge transfer, polarization, and dispersion ingredients. In addition to their occurrence in small-model dimers, these sorts of interactions are a major factor in the structure and function of much larger supramolecular systems [26,27,28,29,30,31,32,33,34,35].…”

Section: Introductionmentioning

confidence: 99%

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Scheiner

2019

Molecules

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Complexes were formed pairing FX, FHY, FH2Z, and FH3T (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) with NH3 in order to form an A⋯N noncovalent bond, where A refers to the central atom. Geometries, energetics, atomic charges, and spectroscopic characteristics of these complexes were evaluated via DFT calculations. In all cases, the A–F bond, which is located opposite the base and is responsible for the σ-hole on the A atom, elongates and its stretching frequency undergoes a shift to the red. This shift varies from 42 to 175 cm−1 and is largest for the halogen bonds, followed by chalcogen, tetrel, and then pnicogen. The shift also decreases as the central A atom is enlarged. The NMR chemical shielding of the A atom is increased while that of the F and electron donor N atom are lowered. Unlike the IR frequency shifts, it is the third-row A atoms that undergo the largest change in NMR shielding. The change in shielding of A is highly variable, ranging from negligible for FSnH3 all the way up to 1675 ppm for FBr, while those of the F atom lie in the 55–422 ppm range. Although smaller in magnitude, the changes in the N shielding are still easily detectable, between 7 and 27 ppm.

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Section: Introductionmentioning

confidence: 99%

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Scheiner

2019

Molecules

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“…[7] Aakeroy et al . [65] In 2019, Kang and co-workers designed catalyst for the Ritter reaction between acetonitrile 47 and (bromomethylene) dibenzene 147 in dichloromethane solvent at room temperature, which leads to the synthesis of N-banzhydrylacetamide 149 (Scheme 64). [66] The mechanism proceeds through the interaction of the catalyst system with (bromomethylene)dibenzene 147 to yield intermediate 150.…”

Section: Using Alkyl or Aryl Halides As Starting Materialsmentioning

confidence: 99%

“…applied N ‐(3‐((( E )‐3‐(iodoethynyl) benzylidene) amino) cyclohexyl)‐1‐(3‐(iodoethynyl) phenyl) methanimine as the catalyst in the non‐classical Ritter reaction of acetonitrile‐d 3 146 with (bromomethylene)dibenzene 147 to prepare N ‐benzhydrylacetamide‐2,2,2‐d 3 148 (Scheme 63). [65] …”

Section: Application Of the Non‐classical Ritter Reaction In The Syntmentioning

confidence: 99%

Recent Applications of Ritter Reactions in Organic Syntheses

2020

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The Ritter reactions are an important Classes of organic reactions in the synthesis of heterocycles and linear amides. Ritter reaction products are pyridine, quinazolinone, and other heterocyclic structures, which have different biological activities such as antibacterial and antivirous application from 2017 to 2020. Furthermore, the Ritter reaction in the synthesis of linear amides is evaluated from 2015 to 2020 in this review. Linear amides are essential components in drug molecules which are difficult to synthesize by conventional methods but can be synthesized through the Ritter reaction.

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“…Halogen bonding (XBing) is increasingly becoming a useful tool in the fields of supramolecular chemistry, crystal engineering and molecular recognition. [1][2][3][4] This non-covalent interaction between an electrophilic region of a covalently bonded halogen atom and a Lewis base has been exploited or identified in a multitude of host-guest, [5] supramolecular, [6] catalytic, [7,8] and biological [9] systems. The increasing adoption and study of the XB in chemical sciences stems from a recognition of the highly directional nature and strength of the interaction, often compared to a hydrogen bond.…”

Section: Introductionmentioning

confidence: 99%

“Click”‐Like η⁶‐Metalation/Demetalation of Aryl Iodides as a Means of Turning “ON/OFF” Halogen Bond Donor Functionality

Kelly

Holman

2022

Angew Chem Int Ed

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η 6 -Metalated aryl halides are recognized as a class of halogen bond (XB) donors. Click-like η 6 -metalation/demetalation of aryl iodides by cyclopentadienylruthenium(II) ([CpRu II ] + ) is shown to turn ON/OFF (amplify/suppress) XB donor functionality. [CpRu(MeCN) 3 ][PF 6 ] is shown to react quantitatively with iodobenzenes (ArI n , n = 1,2) to yield [CpRu-(η 6 -ArI n )][PF 6 ] compounds. Photochemical demetalation (405 nm) quantitatively reverts these compounds to ArI n and [CpRu(MeCN) 3 ][PF 6 ]. Crystal structures of [CpRu-(ArX n )] + salts show that the [CpRu(ArI n )] + cations are strong, charge-assisted XB donors analogous to iodopyridinium cations. XB-induced association of [CpRu-(C 6 H 5 I)] + with diazobicyclo[2.2.2]octane (DABCO) is established by NMR spectroscopy. [CpRu(C 6 H 5 I)]-[BPh 4 ] and [CpRu(1,4-C 6 H 4 I 2 )][BPh 4 ] co-crystallize with DABCO and the structure of [CpRu(1,4-C 6 H 4 I 2 )]-[BPh 4 ]•DABCO•Et 2 O is reported. DFT calculations support amplification of the XBing capabilities of aryl iodides upon [CpRu] + -metalation.

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Organocatalysis by a multidentate halogen-bond donor: an alternative to hydrogen-bond based catalysis

Abstract: Stoichiometric organocatalysis using a charge-neutral bis-iodoethynyl halogen-bond decorated scaffold.

Cited by 26 publications

References 25 publications

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Recent Applications of Ritter Reactions in Organic Syntheses

“Click”‐Like η⁶‐Metalation/Demetalation of Aryl Iodides as a Means of Turning “ON/OFF” Halogen Bond Donor Functionality

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Organocatalysis by a multidentate halogen-bond donor: an alternative to hydrogen-bond based catalysis

Abstract: Stoichiometric organocatalysis using a charge-neutral bis-iodoethynyl halogen-bond decorated scaffold.

Cited by 26 publications

References 25 publications

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

Recent Applications of Ritter Reactions in Organic Syntheses

“Click”‐Like η6‐Metalation/Demetalation of Aryl Iodides as a Means of Turning “ON/OFF” Halogen Bond Donor Functionality

Contact Info

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Resources

About

“Click”‐Like η⁶‐Metalation/Demetalation of Aryl Iodides as a Means of Turning “ON/OFF” Halogen Bond Donor Functionality