B(C6F5)3-Catalyzed transfer 1,4-hydrostannylation of α,β-unsaturated carbonyls using iPr-tricarbastannatrane

Fillion, Eric; Kavoosi, Azadeh; Nguyen, Kevin Tri; Ieritano, Christian

doi:10.1039/c6cc07819b

Cited by 10 publications

(5 citation statements)

References 42 publications

(10 reference statements)

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“…Attempts to trap the transient radicals by reaction with Ph 3 SnH were also undertaken. While 11 B and 19 F NMR spectroscopy suggest weak coordination of B(C 6 F 5 ) 3 with the tin-hydride (Figures S65 and S66 in the SI), 42 addition of Cp* 2 Fe with stirring at room temperature for 12 h gave a suspension containing dark gray and green powders. The dark gray powder showed sparingly solubility in common organic solvents, precluding its formulation.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation

et al. 2017

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Single electron transfer (SET) reactions are effected by the combination of a Lewis acid (e.g., E(CF) E = B or Al) with a small molecule substrate and decamethylferrocene (Cp*Fe). Initially, the corresponding reactions of (PhS) and (PhTe) were shown to give the species [Cp*Fe][PhSB(CF)] 1 and [Cp*Fe][(μ-PhS)(Al(CF))] 2 and [Cp*Fe][(μ-PhTe)(Al(CF))] 3, respectively. Analogous reactions with di-tert-butyl peroxide yielded [Cp*Fe][(μ-HO)(B(CF))] 4 with isobutene while with benzoyl peroxide afforded [Cp*Fe][PhC(O)OE(CF)] (E = B 5, Al 6). Evidence for a radical pathway was provided by the reaction of PhSnH and p-quinone afforded [Cp*Fe][HB(CF)] 7 and [Cp*Fe][(μ-OCH)(E(CF))] (E = B 8, Al 9). In addition, the reaction of TEMPO with Lewis acid and Cp*Fe afforded [Cp*Fe][(CHMeNOE(CF)] (E = B 10, Al 11). Finally, reactions with O, Se, Te and S gave [Cp*Fe][((CF)Al(μ-O)Al(CF))] 12, [Cp*Fe][((CF)Al(μ-Se)Al(CF))] 13, [Cp*Fe][(μ-Te)(Al(CF))] 14 and [Cp*Fe][(μ-S)B(CF))] 15, respectively. The mechanisms of these SET reactions are discussed, and the ramifications are considered.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation

et al. 2017

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“…Starting materials 1d and 1e were prepared according to the reported methods. , Arylmethylene malononitriles 2 were synthesized as reported previously . 5-Benzylidene-1,3-dimethylpyrimidine-2,4,6(1 H ,3 H ,5 H )-trione 5 and ( E )-2-(1-methyl-2-oxoindolin-3-ylidene)acetate 7 were prepared according to reported methods. Solvents were purified prior to use according to the standard procedures.…”

Section: Methodsmentioning

confidence: 99%

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes

Li,

Zhang,

Han

et al. 2023

J. Org. Chem.

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Hepta-2,3,5-trienedioates 1 have been employed as substrates to explore Lewis base-catalyzed annulation reactions. This leads to the discovery of a phosphine-catalyzed [3+2] annulation of 1 with electron-deficient alkenes for the construction of exocyclic olefinic cyclopentenes in good yields and moderate E:Z ratios under mild conditions. The annulation is believed to proceed in a tandem [3+2] cyclization and double bond migration in which the ε-ester is crucial to both processes. This reaction also showcases a substrate-controlled divergent reactivity compared to that of a previous report.

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“…Our design employs the atrane‐type framework [31] and brings three benefits for the establishments of heavier group 14 cation‐based LSAs: 1) stabilization of the cationic center by the intramolecularly transannular N−E (E=Si, Ge, or Sn) bond, 2) orientation of the coordinated site of the cationic center by blocking one of the two apical vacant orbitals of the N−E bond, and 3) facile tuning of steric and electronic factors by changing the aromatic ligands. Although few works to isolate cationic atrane‐type molecules having a group 14 center were reported, [32–34] their use as hard and soft catalytic LSAs remains unexplored. Herein, we report the synthesis and catalytic activity of the atrane‐type molecules 1 E + (E=Si, Ge, or Sn) with a cationic group 14 center (Figure 1B).…”

Section: Figurementioning

confidence: 99%

Synthesis and Catalytic Activity of Atrane‐type Hard and Soft Lewis Superacids with a Silyl, Germyl, or Stannyl Cationic Center

Tanaka

Konishi

Yasuda

2021

Chemistry An Asian Journal

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The synthesis and isolation of atrane‐type molecules 1E+ (E=Si, Ge, or Sn) having a cationic group 14 elemental center are reported. The cations 1E+ act as hard and soft Lewis superacids, which readily interact with various hard and soft Lewis basic substrates. The rigid atrane framework stabilizes the localized positive charge on the elemental center and assists the formation of the well‐defined highly coordinated states of 1E+. The cations were applied to the hydrodefluorination, Friedel‐Crafts reaction, alkyne cyclization, and carbonyl reduction as Lewis acid catalysts. Most notably, [1Si][ClO4] exhibits unique chemoselectivity that depends on a solvent in the competitive reaction of silyl enol ether with a mixture of benzaldehyde dimethyl acetal and benzaldehyde. Our findings indicate the potential of hard and soft Lewis superacids in organic synthesis.

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B(C₆F₅)₃-Catalyzed transfer 1,4-hydrostannylation of α,β-unsaturated carbonyls using iPr-tricarbastannatrane

Cited by 10 publications

References 42 publications

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation

Single Electron Delivery to Lewis Pairs: An Avenue to Anions by Small Molecule Activation

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes

Synthesis and Catalytic Activity of Atrane‐type Hard and Soft Lewis Superacids with a Silyl, Germyl, or Stannyl Cationic Center

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