SF5-Pyridylaryl-λ3-iodonium salts and their utility as electrophilic reagents to access SF5-pyridine derivatives in the late-stage of synthesis

Das, Prajwalita; Takada, Masahiro; Matsuzaki, Kohei; Saito, Nozomu; Shibata, Norio

doi:10.1039/c7cc01043e

Cited by 22 publications

(15 citation statements)

References 69 publications

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“…More and more examples of biologically active SF 5 -containing drug candidates have been reported in recent years (Figure 1c) [35,38,39,40,41,42,43,44]. Extending our research to the design and synthesis of SF 5 -containing biologically attractive molecules [45,46,47,48,49,50,51,52,53,54,55,56,57] and a halogen bonding research program [58,59], we are interested in aryl iodides 1a – d consisting of SF 5 -group(s) in the benzene ring as potential drug fragments capable of halogen bonding, in particular, 3,5-bis-SF 5 -iodobenzene ( 1d , Figure 1d). In this research, we have examined the halogen bonding induced by SF 5 -aryl iodides 1a – d .…”

Section: Introductionmentioning

confidence: 81%

Studies of Halogen Bonding Induced by Pentafluorosulfanyl Aryl Iodides: A Potential Group of Halogen Bond Donors in a Rational Drug Design

Sumii

Sasaki

Tsuzuki³

et al. 2019

Molecules

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The activation of halogen bonding by the substitution of the pentafluoro-λ6-sulfanyl (SF5) group was studied using a series of SF5-substituted iodobenzenes. The simulated electrostatic potential values of SF5-substituted iodobenzenes, the ab initio molecular orbital calculations of intermolecular interactions of SF5-substituted iodobenzenes with pyridine, and the 13C-NMR titration experiments of SF5-substituted iodobenzenes in the presence of pyridine or tetra (n-butyl) ammonium chloride (TBAC) indicated the obvious activation of halogen bonding, although this was highly dependent on the position of SF5-substitution on the benzene ring. It was found that 3,5-bis-SF5-iodobenzene was the most effective halogen bond donor, followed by o-SF5-substituted iodobenzene, while the m- and p-SF5 substitutions did not activate the halogen bonding of iodobenzenes. The similar ortho-effect was also confirmed by studies using a series of nitro (NO2)-substituted iodobenzenes. These observations are in good agreement with the corresponding Mulliken charge of iodine. The 2:1 halogen bonding complex of 3,5-bis-SF5-iodobenzene and 1,4-diazabicyclo[2.2.2]octane (DABCO) was also confirmed. Since SF5-containing compounds have emerged as promising novel pharmaceutical and agrochemical candidates, the 3,5-bis-SF5-iodobenzene unit may be an attractive fragment of rational drug design capable of halogen bonding with biomolecules.

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Section: Introductionmentioning

confidence: 81%

Studies of Halogen Bonding Induced by Pentafluorosulfanyl Aryl Iodides: A Potential Group of Halogen Bond Donors in a Rational Drug Design

Sumii

Sasaki

Tsuzuki³

et al. 2019

Molecules

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“…The same year, Shibata reported a metal-free late-stage pentafluorosulfanyl (SF 5 ) pyridylation of unprotected and N -methyl pyrroles using a novel designed electrophilic heteroaryliodonium triflates [ 61 ]. The reaction took place at the C2 position using SF 5 -pyridylmesityl-λ 3 -idoanes under the same reaction conditions reported by Kita (NaOH in pyrrole) giving the expected bi-heteroaryl products in yields ranging from 44% to 98% ( Scheme 4 ).…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Transition-Metal-Free Late-Stage C-H and N-H Arylation of Heteroarenes Using Diaryliodonium Salts

Besson

Fruit

2021

Pharmaceuticals

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Transition-metal-free direct arylation of C-H or N-H bonds is one of the key emerging methodologies that is currently attracting tremendous attention. Diaryliodonium salts serve as a stepping stone on the way to alternative environmentally friendly and straightforward pathways for the construction of C-C and C-heteroatom bonds. In this review, we emphasize the recent synthetic advances of late-stage C(sp2)-N and C(sp2)-C(sp2) bond-forming reactions under metal-free conditions using diaryliodonium salts as arylating reagent and its applications to the synthesis of new arylated bioactive heterocyclic compounds.

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“…Among these significant works, hypervalent iodine reagents have been widely used as ideal and highly efficient oxidants or reaction partners (Kita et al, 1994 ; Nasrallah et al, 2019 ) due to their superior bench stability, high reactivity, low toxicity, environmental friendliness, ease of operation, and ready availability (Dohi et al, 2009 ; Sun and Shi, 2014 ). For instance, diverse iodine(III) reagents were invented to introduce fluorinated group into organic molecules (Yang et al, 2013 ; Matsuzaki et al, 2014 ; Suzuki et al, 2014 ; Das and Shibata, 2017 ; Das et al, 2017 ; Wang et al, 2017 ). Because of the large size of iodine atoms, a linear three-center, four-electron (3c-4e) bond (L–I–L) which uses a non-hybridized 5p orbital of iodine atom is formed.…”

Section: Introductionmentioning

confidence: 99%

The C3-H Bond Functionalization of Quinoxalin-2(1H)-Ones With Hypervalent Iodine(III) Reagents

et al. 2020

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The modification of quinoxalin-2(1H)-ones via direct C-H bond functionalization has begun to receive widespread attention, due to quinoxalin-2(1H)-one derivatives' various biological activities and pharmaceutical properties. This mini review concentrates on the accomplishments of arylation, trifluoromethylation, alkylation, and alkoxylation of quinoxalin-2(1H)-ones with hypervalent iodine(III) reagents as reaction partners or oxidants. The reaction conditions and mechanisms are compared and discussed in detail.

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SF₅-Pyridylaryl-λ³-iodonium salts and their utility as electrophilic reagents to access SF₅-pyridine derivatives in the late-stage of synthesis

Cited by 22 publications

References 69 publications

Studies of Halogen Bonding Induced by Pentafluorosulfanyl Aryl Iodides: A Potential Group of Halogen Bond Donors in a Rational Drug Design

Studies of Halogen Bonding Induced by Pentafluorosulfanyl Aryl Iodides: A Potential Group of Halogen Bond Donors in a Rational Drug Design

Recent Advances in Transition-Metal-Free Late-Stage C-H and N-H Arylation of Heteroarenes Using Diaryliodonium Salts

The C3-H Bond Functionalization of Quinoxalin-2(1H)-Ones With Hypervalent Iodine(III) Reagents

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