Anomalous Staudinger reaction at intramolecular frustrated P–B Lewis pair frameworks

Stute, Annika; Heletta, Lukas; Fröhlich, Roland; Daniliuc, Constantin G.; Kehr, Gerald; Erker, Gerhard

doi:10.1039/c2cc36782c

Cited by 59 publications

(38 citation statements)

References 46 publications

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“…[ 85] In contrast to 8, 97 does not exhibit any significant phosphorus Lewis base/boron Lewis acid interaction as evidenced by NMR spectroscopic data (97: 11 B d =+ 67.8, 31 P d = À32.5). Nonetheless, both compounds 97 and 8 react with mesitylazide.…”

Section: Intramolecular Flp Systemsmentioning

confidence: 98%

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Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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Frustrated Lewis pairs (FLPs) are combinations of Lewis acids and Lewis bases in solution that are deterred from strong adduct formation by steric and/or electronic factors. This opens pathways to novel cooperative reactions with added substrates. Small-molecule binding and activation by FLPs has led to the discovery of a variety of new reactions through unprecedented pathways. Hydrogen activation and subsequent manipulation in metal-free catalytic hydrogenations is a frequently observed feature of many FLPs. The current state of this young but rapidly expanding field is outlined in this Review and the future directions for its broadening sphere of impact are considered.

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Section: Intramolecular Flp Systemsmentioning

confidence: 98%

“…Anomalous Staudinger oxidation of the mesityl azide addition product of 8 is achieved by photolysis. [85] Scheme 38. Activation barriers of ring opening in intramolecular FLPs.…”

Section: Intramolecular Flp Systemsmentioning

confidence: 99%

Frustrated Lewis Pair Chemistry: Development and Perspectives

2015

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“…[12] Related is the reactivity of frustrated Lewis pairs (FLPs) [13] towards organic azides, buti nt his case multiple Staudinger intermediates have been isolated. Phosphorus/boron-based FLPs have been shown to add to the a-nitrogen of the azide form-ing coordinationm ode D (Figure 1) [14] and, in one case, it was found that upon irradiation this speciesr earranges to a,b-nitrogen adduct E. [15] The a,g-nitrogen coordinationm ode F was found by treatingageminal FLP with mesityl azide. [16,17] In analogy to the reactivityo fN HCs (C;F igure 1), dinitrogen elimination occurs when TMS azide was reacted with aP /Al-based FLP affording heterocycle G, [18] yet in this case no follow-up chemistry has been investigated.…”

Section: Introductionmentioning

confidence: 99%

New Insights in Frustrated Lewis Pair Chemistry with Azides

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Jupp

Nieger

et al. 2019

Chemistry A European J

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The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl‐, mesityl‐, and tert‐butyl azide affording, respectively, six, five, and four‐membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six‐membered ring structure, which is thermally stable with an N‐phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four‐membered heterocycle (5), which can be considered as a formal FLP‐trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

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“…Dieser Reaktionstyp kann als eine Jacobsen‐artige Indazolbildung beschrieben werden, die normalerweise von Diazoestern der allgemeinen Formel “Ar‐NN‐OR” ausgeht 17. Eine ähnliche Reaktivität wurde von Erker bei einem fünfgliedrigen C 2 BNP‐Heterocyclus beobachtet, bei dem das terminale Stickstoffatom von Mesitylazid auf gleiche Weise in den Ring eingebunden ist 18. Außerdem stellte sich bei der Analyse der Daten einer Röntgenstrukturanalyse von 5 im Festkörper heraus, dass die asymmetrische Einheit nicht nur 5 sondern auch etwa 10 % der Folgeprodukte 6 und 7 enthält (Abbildung S9).…”

Section: Methodsunclassified

Synthese BN‐isosterer Verbindungen von Azofarbstoffen durch Ringerweiterung von Borolen mit Aziden

et al. 2015

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Wir stellen hier die Ergebnisse unserer Untersuchungen bezüglichd es Effekts der ortho-Substitution von Arylaziden auf die Ringerweiterung von Borolen, fünfgliedri-gen, ungesättigten Borheterocyclen, vor.D ie Studien führten zu der Isolierung der ersten 1,2-Azaborinin-substituierten Azofarbstoffe,bei denen es sich um leuchtend gelbe Feststoffe handelt. In Lçsung stellte sich eines der Derivate,( E)-2-Mesityl-1-(mesityldiazenyl)-3,4,5,6-tetraphenyl-1,2-azaborinin, als nichtstabil heraus,sondern geht eine Jacobsen-Reaktion zu einem Indazol und einem 1-Hydro-1,2-azaborinin ein. Um den Mechanismus der unerwarteten Bildung der Azo-Azaborinine nachvollziehen zu kçnnen und um Rückschlüsse auf die Rolle der ortho-Substitution auf den Reaktionsverlauf zu ziehen, wurden Dichtefunktionalrechnungen durchgeführt.

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Anomalous Staudinger reaction at intramolecular frustrated P–B Lewis pair frameworks

Cited by 59 publications

References 46 publications

Frustrated Lewis Pair Chemistry: Development and Perspectives

Frustrated Lewis Pair Chemistry: Development and Perspectives

New Insights in Frustrated Lewis Pair Chemistry with Azides

Synthese BN‐isosterer Verbindungen von Azofarbstoffen durch Ringerweiterung von Borolen mit Aziden

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