Recent advances and applications of reductive desulfurization in organic synthesis

Rentner, Jana; Kljajic, Marko; Offner, Lisa; Breinbauer, Rolf

doi:10.1016/j.tet.2014.06.104

Cited by 58 publications

(37 citation statements)

References 159 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7 Hydrodesulfurization, i.e., cleaving the C-S bond to form C-H bond, plays an importance role in manufacturing nonpolluting fuel from natural resources. 8,9 As early as 1940s, several Ni-mediated hydrodesulfurization reactions were reported with a large excess of Raney nickel as the reducing agent.…”

mentioning

confidence: 99%

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

et al. 2017

View full text Add to dashboard Cite

The reaction mechanism of Ni(COD) 2 catalyzed hydrodesulfurization of aryl sulfide PhSMe with HSiMe 3 as the reducing agent has been studied by using density functional theory methods. Both PhSMe-coordinated pathway and "ligandless" pathway have been identified and compared. It is found that these two reaction pathways are kinetically competitive and the s-complex assisted metathesis (s-CAM) transition state is the highest point on each energy profile for both pathways. Moreover, both the singlet and triplet reaction pathways of ligand substitutions have been compared and found that both singlet and triplet reaction mechanisms are competitive for the ligand substitution of COD with PhSMe on PhSMecoordinated pathway while the triplet mechanism holds a distinct advantage over singlet one for that of COD with HSiMe 3 on "ligandless" pathway.

show abstract

mentioning

confidence: 99%

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

et al. 2017

View full text Add to dashboard Cite

show abstract

“…In principle, the development of cross‐coupling and C−H activation chemistry of the sensitive isothiazole ring prone to reductive N−S cleavage is of high synthetic value and opens the door to a fundamentally new concept for the synthesis of complex isothiazoles with potential applications in medicinal chemistry and materials science.…”

Section: Reactivity Of Isothiazolesmentioning

confidence: 99%

“…Furthermore, the synthetic community has embraced isothiazoles as valuable α,β‐unsaturated imine equivalents that can be revealed under mild reductive cleavage conditions . Historically, one of the first examples of the use of the isothiazole ring as a masked template in complex natural product synthesis was reported by R. B. Woodward (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis and Reactivity of Isothiazoles

2019

View full text Add to dashboard Cite

Isothiazoles represent an important class of five‐membered sulfur heterocycles that are widely utilized in medicinal chemistry and organic synthesis due to the unique properties of two electronegative heteroatoms in a 1,2‐relationship. However, in contrast to other 1,2‐azoles, the facile assembly of isothiazoles has always been considered a substantial challenge. In the last decade, major advances have taken place in the fields of synthesis and functionalization of isothiazoles that make them accessible to a wide range of interested chemists through unprecedented pathways. New condensation methods have emerged that address the challenges posed by unstable thiohydroxylamine. New metal‐catalyzed approaches have been reported that deliver densely decorated isothiazoles bearing various sensitive functional groups. New functionalization strategies have been developed through both cross‐coupling and direct C−H activation chemistry. Finally, the emergence of novel heterocyclic architectures based on isothiazole opens the door for future investigations of this versatile heterocyclic scaffold. This review covers the period from January 2004 to December 2018 and is intended as a sequel to the review on isoxazoles, which represent another class of synthetically‐important 1,2‐azoles (see Adv. Synth. Catal. 2015, 357, 2583–2614).

show abstract

“…Although a complete mechanism for desulfurisation by RANEY® nickel remains unclear, 25,26 we explored a number of avenues to try to understand the atom efficiency of the reaction, as well as the source of the formyl hydrogen atom. First, although we did not attempt to dry the pyrophoric reductant, water from the commercially available RANEY® nickel slurry was manually removed by pipette.…”

mentioning

confidence: 99%

“…The manner by which RANEY® nickel effects desulfurative reduction has been long debated. 25,26,29 Assuming a radical mechanism, we used two radical clocks/traps in the hopes of intercepting radical intermediate species (Fig. 2).…”

mentioning

confidence: 99%

Synthesis and reactivity of 2-thionoester pyrroles: a route to 2-formyl pyrroles

et al. 2019

View full text Add to dashboard Cite

show abstract

Recent advances and applications of reductive desulfurization in organic synthesis

Cited by 58 publications

References 159 publications

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

Recent Advances in the Synthesis and Reactivity of Isothiazoles

Synthesis and reactivity of 2-thionoester pyrroles: a route to 2-formyl pyrroles

Contact Info

Product

Resources

About