Catalytic synthesis of sulfur and phosphorus compounds via atom-economic reactions

Kawaguchi, Shinichi; Yamamoto, Yuki

doi:10.1016/j.mencom.2020.03.001

Cited by 18 publications

(12 citation statements)

References 116 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds has recently attracted wide attention as an atomically efficient method for carbon-heteroatom bond formation [1][2][3][4][5][6]. This addition reaction is promoted by transition-metal catalysts, acids, bases, and radical initiators [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. On the other hand, photoirradiation has recently attracted much attention as a clean, ecofriendly, and powerful method in organic synthesis [27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

et al. 2022

Self Cite

View full text Add to dashboard Cite

The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (1), to stereoselectively obtain the corresponding (E)-vic-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing 1 and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent trans-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.

show abstract

Section: Introductionmentioning

confidence: 99%

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…Given the prevalence of sulfur in biologically relevant organic molecules, − inventing methods to forge C–S bonds remains a worthwhile pursuit. − Hydrothiolation, the addition of a thiol across a degree of unsaturation, represents a straightforward and atom economical way of building molecules with sulfide functional groups. − In previous communications, , our laboratory disclosed highly regioselective hydrothiolations of conjugated dienes, where regiocontrol was achieved through careful selection of the counterion associated with the Rh-catalyst (Figure A). Using a noncoordinating counterion, such as SbF 6 – , allows the conjugated diene to bind the catalyst in an η 4 fashion en route to allylic sulfide products .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control

Nie

Kuker

et al. 2021

J. Am. Chem. Soc.

View full text Add to dashboard Cite

In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictates whether the pathway involves ring-retention or ring-opening. Mechanistic studies reveal the origin for this switchable selectivity. Our results suggest the two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from this intermediate to afford cyclopropyl sulfides in high enantio-and diastereoselectivities. Alternatively, atropisomeric ligands (such as DTBM-BINAP) enable ring-opening from the cyclopropyl-Rh(III) intermediate to generate allylic sulfides with high enantio-and regiocontrol.

show abstract

“…This process usually occurs via radical, nucleophilic, or catalytic pathways [23][24][25][26]. Today, systems based on Cu-, Ni-, or Pd-complexes find wide application in the hydrothiolation process [27][28][29][30] as well as other reactions of C-S bond formation [31][32][33][34]. Taking into account the high practical demand in metal-catalyzed methodology, a catalytic reaction driven by transition metals was studied.…”

Section: Introductionmentioning

confidence: 99%

ESI-MS Analysis of Thiol-yne Click Reaction in Petroleum Medium

2021

View full text Add to dashboard Cite

Petroleum contains a large number of heteroatomic compounds, but today, most of them are not efficiently utilized. The constant development of the sustainability concept recalls for rethinking the usage of fossil resources with improved chemical utility. In order to initiate research aimed at involving active petroleum compounds in chemical transformations, a new analytical method for product detection is needed. Here, we study the click reaction of thiols with alkynes, leading to the formation of α-vinyl sulfides directly in the petroleum environment. The reaction was carried out using an (IMes)Pd(acac)Cl catalyst, which demonstrated tolerance to petroleum components. In this study, the concentration of thiols ranged from 1 M to 0.01 M (from 8% to 0.1%). To detect products at low concentrations, a special alkyne labeled with an imidazole moiety was used. This approach made it possible to observe the formation of vinyl sulfides by electrospray ionization mass spectrometry (ESI-MS), which provides an opportunity for further optimization of the reaction conditions and future developments for the direct involvement of oil components in chemical reactions.

show abstract

Catalytic synthesis of sulfur and phosphorus compounds via atom-economic reactions

Cited by 18 publications

References 116 publications

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization

Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control

ESI-MS Analysis of Thiol-yne Click Reaction in Petroleum Medium

Contact Info

Product

Resources

About