Organocatalytic, difluorocarbene-based S-difluoromethylation of thiocarbonyl compounds

Fuchibe, Kohei; Bando, Masaki; Takayama, Ryo; Ichikawa, Junji

doi:10.1016/j.jfluchem.2014.08.013

Cited by 30 publications

(13 citation statements)

References 53 publications

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“…150 Classical and routinely used methods to prepare difluoromethylthioethers employ appropriate thiolates and "CF 2 " species, [151][152][153] which is in most cases difluorocarbene (Scheme 28a, left). [154][155][156][157][158][159][160][161][162][163][164][165][166] These early methods suffer from a limited substrate scope and low step economy due to the harsh conditions and stepwise assembly of the -SCF 2 H moiety. In light of these issues, the Goo en group took a step forward to extend the scope by employing the Langlosis β type nucleophilic displacement of thiocyanates (-SCN) by TMSCF 2 H (Scheme 28a, right).…”

Section: Photo-induced C Sp2 -H Difluoromethylthiolation: Synthesis Omentioning

confidence: 99%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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Chemistry has always had as a target the conversion of molecules into valuable materials. Nevertheless, the aim of past synthesis has primarily focused on achieving a given transformation, regardless of the environmental impact of the synthetic route. Given the current global situation, the demand for sustainable alternatives has substantially increased. Our group focuses on developing selective chemical transformations that benefit from mild conditions, improved atom economy, and that can make use of renewable feedstocks as starting materials. This account summarizes our work over the past two decades specifically regarding the selective removal, conversion, and addition of functional groups that can, later on, be applied at a late stage for the modification of complex molecules.

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Section: Photo-induced C Sp2 -H Difluoromethylthiolation: Synthesis Omentioning

confidence: 99%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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“…Screening reaction conditions for the difluoromethylation of the activated X-H bond a Reaction conditions: 2a (0.6 mmol) and 1 in solvent (3 mL). b Determined by19 F NMR with trifluoromethylbenzene as the internal standard.…”

mentioning

confidence: 99%

Difluoromethylation and gem-difluorocyclopropenation with difluorocarbene generated by decarboxylation

et al. 2015

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“…In coordination chemistry, pincer-type ligands containing thio-amide motif have already exhibited their 4 incomparable chelating ability to the selected transition-metals, and their corresponding complexes have been applied in various areas such as chemical-sensor materials, tunable redox-potential complexes, polymer hybrid luminescence materials, building blocks for multinuclear com-plexes, and catalysts for cross-coupling reactions [23][24][25][26][27][28][29][30]. The thio-substitution of amides with LR is an efficient and straightforward method, either the availability of amide substrates, LR, or the reaction condition [7,8,[31][32][33][34][35]. With thio-substitution of amides as a model, we herein reported an efficient work-up procedure of applying LR by utilizing ethylene glycol to decompose the compound A (Figure 2).…”

Section: Figure 1 Generation Of the Six-membered By-product Amentioning

confidence: 99%

A Column-Free and Aqueous Waste-Free Process for Thioamide Preparation with Lawesson’s reagent

Ke¹,

Ling²,

Ding³

et al. 2020

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After completing thio-substitution with the Lawesson’s reagent, ethanol was found to be able to efficiently decompose the inherent stoichiometric six-membered-ring by-product from the Lawesson’s reagent to a highly polarized diethyl thiophosphate. This treatment could significantly simplify the following column purification of the desired thioamide in a small scale preparation. As scaling up the preparation of two pincer-type thioamides, we have successfully developed a convenient process with ethylene glycol to replace ethanol during the workup, including traditional phase-cut, extraction, and re-crystallization. The newly developed column-free procedure did not generate P-contained aqueous waste, and only organic effluents were discharged. It was believed that the optimized procedure can greatly provide opportunity of the application of the Lawesson’s reagent for various thio-substituted reacions in scaling up preparation.

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Organocatalytic, difluorocarbene-based S-difluoromethylation of thiocarbonyl compounds

Cited by 30 publications

References 53 publications

Exploration of new reaction tools for late-stage functionalization of complex chemicals

Exploration of new reaction tools for late-stage functionalization of complex chemicals

Difluoromethylation and gem-difluorocyclopropenation with difluorocarbene generated by decarboxylation

A Column-Free and Aqueous Waste-Free Process for Thioamide Preparation with Lawesson’s reagent

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