Pd-Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates

Smyth, Lynette A.; Phillips, Eric M.; Chan, V. S.; Napolitano, José G.; Henry, Rodger F.; Shekhar, Shashank

doi:10.1021/acs.joc.5b02523

Cited by 45 publications

(18 citation statements)

References 71 publications

(130 reference statements)

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“…In 2016, Shekhar’s group finally succeeded in the trifluoromethanesulfonylation of the more readily available (het)aryl triflates and some aryl chlorides using a combination of Pd 2 (dba) 3 and the bulky RockPhos phosphine ligand in toluene and tris(3,6-dioxaheptyl)amine (TDA) as phase-transfer catalyst to facilitate the reaction with the sparingly soluble CF 3 SO 2 Na ( Scheme 86 ) [ 124 ].…”

Section: Reviewmentioning

confidence: 99%

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

Guyon¹,

Cahard²

2017

Beilstein J. Org. Chem.

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Sodium trifluoromethanesulfinate, CF3SO2Na, and trifluoromethanesulfonyl chloride, CF3SO2Cl, are two popular reagents that are widely used for the direct trifluoromethylation of a large range of substrates. Further, these two reagents are employed for the direct trifluoromethylsulfenylation and trifluoromethylsulfinylation, the introduction of the SCF3 and the S(O)CF3 group, respectively. In addition to the aforementioned reactions, the versatility of these two reagents is presented in other reactions such as sulfonylation and chlorination. This first part is dedicated to sodium trifluoromethanesulfinate.

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Section: Reviewmentioning

confidence: 99%

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

Guyon¹,

Cahard²

2017

Beilstein J. Org. Chem.

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“…In the third pathway of allorecognition, the “semi‐direct,” recipient APCs acquire intact donor MHC molecules and present to recipient T cells with direct allospecificity 2 . We have recently demonstrated in a mouse model of skin transplant that the semi‐direct pathway lasts for the entire duration of the life of the transplant, implying that the direct recognition of donor alloAgs plays a role not only early posttransplant but also at late time points posttransplant 3 . Recently, Morelli et al and Marino et al have suggested that “cross‐dressing” of recipient dendritic cells (DCs) with donor MHC molecules via the acquisition of extracellular vesicles (EVs), is the main contributor of priming of the direct alloresponse in skin graft rejection early posttransplant 4,5 …”

Section: Introductionmentioning

confidence: 99%

B lymphocytes contribute to indirect pathway T cell sensitization via acquisition of extracellular vesicles

Becker

Ratnasothy

Sen

et al. 2021

American Journal of Transplantation

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B cells have been implicated in transplant rejection via antibody‐mediated mechanisms and more recently by presenting donor antigens to T cells. We have shown in patients with chronic antibody‐mediated rejection that B cells control the indirect T cell alloresponses. To understand more about the role of B cells as antigen‐presenting cells for CD4+ T cell with indirect allospecificity, B cells were depleted in C57BL/6 mice, using an anti‐CD20 antibody, prior to receiving MHC class I–mismatched (Kd) skin. The absence of B cells at the time of transplantation prolonged skin graft survival. To study the mechanisms behind this observation, T cells with indirect allospecificity were transferred in mice receiving a Kd skin transplant. T cell proliferation was markedly inhibited in the absence of recipient B cells, suggesting that B cells contribute to indirect pathway sensitization. Furthermore, we have shown that a possible way in which B cells present alloantigens is via acquisition of MHC‐peptide complexes. Finally, we demonstrate that the addition of B cell depletion to the transfer of regulatory T cells (Tregs) with indirect alloresponse further prolonged skin graft survival. This study supports an important role for B cells in indirect T cell priming and further emphasizes the advantage of combination therapies in prolonging transplant survival.

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“…Common methods [19] for preparing aryl triflones include oxidation of the corresponding aryl sulfides, trifluoromethylation of aryl sulfonyl fluorides or aryl sulfonates, direct trifluoromethanesulfonylation of aromatic compounds, and thia‐Fries rearrangement of aryl trifluoromethanesulfonates. Yet, the direct introduction of triflyl group onto aromatic rings is still a challenge [19,29–33] . Several of these methods have been tested in our group for the synthesis of ( R )‐6,6′‐Tf 2 ‐BINOL 1 with a variable degree of success.…”

Section: Resultsmentioning

confidence: 99%

(R)‐BINOL‐6,6’‐bistriflone: Shortened Synthesis, Characterization, and Enantioselective Catalytic Applications

et al. 2021

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The title compound, characterized by X‐ray crystallography, was accessed in 4 steps with 92 % ee. and 25 % yield from an O‐protected (R)‐BINOL precursor. This revised synthetic route relied on a chlorosulfonylation reaction, as a shortcut to a previously developed sequence requiring the use of toxic SO2 gas and bromine. The strongly electron‐impoverished (R)‐6,6′‐Tf2‐BINOL proved an effective ligand in metal‐catalyzed enantioselective transformations such as a Zr‐based Mannich‐type reaction. The catalytic species was characterized by X‐ray crystallography as a unique tetrameric metal cluster. The 6,6′‐bistriflone groups also allowed to exalt the H‐bond donor capacity of the BINOL moiety, as illustrated in an organocatalyzed Morita‐Baylis‐Hillman transformation. Theoretical study indicated that the 6,6′‐bistriflone groups induce a drop of the phenol acidity of 5 pKa units in DMSO. Overall, this work simplified the access, completed the characterization, and confirmed the potential of (R)‐6,6′‐Tf2‐BINOL as a promising platform to further elaborate activated chiral metal ligands or organocatalysts.

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Pd-Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates

Cited by 45 publications

References 71 publications

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

B lymphocytes contribute to indirect pathway T cell sensitization via acquisition of extracellular vesicles

(R)‐BINOL‐6,6’‐bistriflone: Shortened Synthesis, Characterization, and Enantioselective Catalytic Applications

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Pd-Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates

Cited by 45 publications

References 71 publications

CF3SO2X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF3SO2Na

CF3SO2X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF3SO2Na

B lymphocytes contribute to indirect pathway T cell sensitization via acquisition of extracellular vesicles

(R)‐BINOL‐6,6’‐bistriflone: Shortened Synthesis, Characterization, and Enantioselective Catalytic Applications

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Product

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CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na

CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CF₃SO₂Na