Contrasting Frustrated Lewis Pair Reactivity with Selenium‐ and Boron‐Based Lewis Acids

Wilkins, Lewis C.; Günther, Benjamin; Walther, Melanie; Lawson, James R.; Wirth, Thomas; Melen, Rebecca L.

doi:10.1002/anie.201605239

Cited by 37 publications

(17 citation statements)

References 72 publications

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“…Alternatively,b orane activation of the alkyne followed by a1 ,2-trans-oxyboration reaction with subsequent proto-or carbodeboration could occur (pathway II,S cheme 6). Both pathways have been observed in other reactions with B(C 6 F 5 ) 3 .F or example,w eh ave previously noted the deprotection of Boc groups using catalytic amounts of B(C 6 F 5 ) 3 , which is reminiscent of pathway I, [20] while oxyboration pathway II has also been observed in studies by ourselves [20,21] and others [10b, 22] in the synthesis of oxazoles,d ioxaborinines, pyryliums,and lactones.…”

Section: Angewandte Chemiementioning

confidence: 99%

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates

2017

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This work showcases a new catalytic cyclization reaction using a highly Lewis acidic borane with concomitant C-H or C-C bond formation. The activation of alkyne-containing substrates with B(C F ) enabled the first catalytic intramolecular cyclizations of carboxylic acid substrates using this Lewis acid. In addition, intramolecular cyclizations of esters enable C-C bond formation as catalytic B(C F ) can be used to effect formal 1,5-alkyl migrations from the ester functional groups to unsaturated carbon-carbon frameworks. This metal-free method was used for the catalytic formation of complex dihydropyrones and isocoumarins in very good yields under relatively mild conditions with excellent atom efficiency.

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Section: Angewandte Chemiementioning

confidence: 99%

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates

2017

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“…[104][105][106][107][108][109][110] Subsequent work by the groups of Melen, Stephan, Paradies, and Hashmi has demonstrated that strongly Lewis acidic boranes can be utilized to induce a wealth of intramolecular cyclization reactions involving propargyl esters 111,112 amides, 113 and related systems where an activated alkyne is attacked by an internal nucleophile. [114][115][116][117][118][119][120][121][122][123][124][125] Such reactions in many cases mirror transformations accessible typically via carbophillic Au or Pt catalysts. 103 An exemplary cyclization of a 1,5-enyne 115 is presented in Figure 8, which may be accessed via either boron-or gold-based catalysis.…”

Section: Alkynesmentioning

confidence: 99%

Metallomimetic Chemistry of Boron

2019

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The study of main-group molecules that behave and react similarly to transition metal (TM) complexes has attracted significant interest in the recent decades. Most notably, the attractive idea of eliminating the all-too-often rare and costly metals from catalysis has motivated efforts to develop main-group-element-mediated reactions. Main-group elements, however, lack the electronic flexibility of many TM complexes that arise from combinations of empty and filled d-orbitals and that seem ideally suited to bind and activate many substrates. In this Review, we look at boron, an element which, despite its non-metal nature, low atomic weight, and relative redox staticity has achieved great milestones in terms of TM-like reactivity. We show how in inter-element cooperative systems, diboron molecules and hypovalent complexes, the fifth element can acquire a truly metallomimetic character. As we discuss, this character is particularly strikingly demonstrated by the reactivity of boron-based molecules with H2, CO, alkynes, alkenes and even with N2.

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“…The different reaction conditions, solvents and catalysts used for constructions of 4-SÀ (Se, Te)-isochromenones 55 is summarized in Scheme 19. [50][51][52][53] Synthesis of 3-organoselanylchromone 57 was successfully achieved via iron(III) chloride and diorganyl diselenides 4 promoted intramolecular 6-endodig cyclization of alkynyl aryl ketone derivatives 56.…”

Section: Synthesis Of 4-organochalconylisochromenone and 3-organochalmentioning

confidence: 99%

Synthesis of Seleno‐Heterocycles via Electrophilic/Radical Cyclization of Alkyne Containing Heteroatoms

Sonawane

Ninomiya

et al. 2020

Adv Synth Catal

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containing heterocyclic scaffolds by virtue of their interesting reactivities and a broad range of applications in the medicinal and materials chemistry. This review involves the electrophilic/radical cyclization of alkynes containing heteroatoms which resulted into the novel Se‐heterocycles. The synthesis of seleno‐heterocycles via different nucleophiles including O, N, S, Se, Te, and C‐nucleophiles is exhaustively discussed. Also, one‐pot electrophilic cyclization of 1,3‐diynes and 1,3,5‐triynes was described in details. Furthermore, the various mechanisms underlying the synthesis of selenium‐β‐lactam, carbapenem heterocycle, bis‐ and tris‐selenide alkene, β‐selenosulfonation and selenated alkynes were discussed. The Se‐heterocycles reported in this review allow preparing these selenated compounds bearing the selenium moiety both on the rings (outside) and inside the ring (e. g. selenophenes). The review demonstrates the growing opportunities to construct selenium containing heterocycles from alkynes containing heteroatoms.

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Contrasting Frustrated Lewis Pair Reactivity with Selenium‐ and Boron‐Based Lewis Acids

Cited by 37 publications

References 72 publications

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates

Metallomimetic Chemistry of Boron

Synthesis of Seleno‐Heterocycles via Electrophilic/Radical Cyclization of Alkyne Containing Heteroatoms

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Contrasting Frustrated Lewis Pair Reactivity with Selenium‐ and Boron‐Based Lewis Acids

Cited by 37 publications

References 72 publications

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C6F5)3 via Cationic Intermediates

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C6F5)3 via Cationic Intermediates

Metallomimetic Chemistry of Boron

Synthesis of Seleno‐Heterocycles via Electrophilic/Radical Cyclization of Alkyne Containing Heteroatoms

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Product

Resources

About

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates

Stoichiometric and Catalytic C−C and C−H Bond Formation with B(C₆F₅)₃ via Cationic Intermediates