Heteroatom directed photoarylation. Synthetic potential of the heteroatom oxygen

Schultz, Arthur G.; Lucci, Robert D.; Fu, Wallace Y.; Berger, Mitchell H.; Erhardt, Jeanette M.; Hagmann, William K.

doi:10.1021/ja00475a028

Cited by 59 publications

(16 citation statements)

References 7 publications

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“…meta ‐Substituents on cyclohexenone‐derived aryloxy substrates generally cyclize to give regioisomeric ratios in which the 7‐isomer is the minor product: 9/7‐methyl 11 (91 % combined yield, ratio 2.2:1) and 9/7 dimethylamino 12 (68 % combined yield, ratio 2.3:1). It is worth noting that electron‐rich substrates efficiently cyclize to products such as 12 in high yields; under high intensity UV irradiation this cyclization does not proceed . Symmetrical disubstituted substrates cyclize effectively whether electron donating ( 13 , 94 % yield) or electron withdrawing ( 14 , 92 % yield).…”

Section: Methodsmentioning

confidence: 99%

Visible Light Photocatalysis of 6π Heterocyclization

et al. 2017

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Photo-mediated 6p cyclization is avaluable method for the formation of fused heterocyclic systems.H ere we demonstrate that irradiation of cyclic 2-aryloxyketones with blue LED light in the presence of an Ir III complex leads to efficient and high yielding arylation across ap anoply of substrates by energy transfer.2 -Arylthioketones and 2-arylaminoketones also cyclizee ffectively under these conditions. Quantum calculation demonstrates that the reaction proceeds via conrotatory ring closure in the triplet excited state. Subsequent suprafacial 1,4-hydrogen shift and epimerization leads to the observed cis-fused products.

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Section: Methodsmentioning

confidence: 99%

Visible Light Photocatalysis of 6π Heterocyclization

et al. 2017

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“…Consequently,a lternative Lewis acids were investigated that could be chelated by the carbonyl and aryloxy oxygen atoms. The[ 6 p]p hotocyclization of substrates 18 [29,30] was relatively unexplored at the time and was therefore chosen as am odel reaction for enantioselective photochemistry starting from a-substituted enones 18 (Scheme 12). [31] As expected, ac onsiderable bathochromic shift was observed with EtAlCl 2 as the Lewis acid.…”

Section: Angewandte Chemiementioning

confidence: 99%

Chromophore Activation of α,β‐Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions

2018

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The first law of photochemistry, as described by Theodor von Grotthuß and John W. Draper, states that only the light absorbed by the irradiated matter can effect photochemical change. Consequently, the photochemical behavior of a molecule can be controlled by bringing its absorbance properties in line with the emission of the light source. A compound with a chromophore that only absorbs light at short wavelengths will not be excited by light of longer wavelengths. If one can reversibly modify the photophysical properties of a compound with a chemical activator, then it is possible to photoexcite only the activated species. For α,β‐unsaturated carbonyl compounds, the use of Lewis acids, Brønsted acids, or the formation of the respective iminium ions can bring about the desired chromophore activation to catalyze a photochemical reaction at a given wavelength. In this Minireview, the concept of chromophore activation will be illustrated, and examples of its implementation in enantioselective catalysis will be discussed.

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“…Schema 10), weshalb in diesem Fall andere Lewis-Säuren ins Auge gefasst wurden. Die Chance, über einen Aryloxysubstituenten eine Chelatisierung zu erreichen, und die zu diesem Zeitpunkt noch nicht intensiv untersuchte [6p]-Photocyclisierung der Substrate 18 [29,30] waren die Gründe füre ine umfangreichere Studie mit dieser Substanzklasse (Schema 12). [31] Die erwartete bathochrome Verschiebung mit einer Lewis-Säure (EtAlCl 2 )w ar sehr gut zu erkennen.…”

Section: -Alkenone Und 2-alkensäureamideunclassified

Chromophoraktivierung von α,β‐ungesättigten Carbonylverbindungen und ihre Anwendung in enantioselektiven Photoreaktionen

2018

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Das erste Gesetz der Photochemie, das auf Theodor von Grotthuß und John W. Draper zurückgeht, besagt, dass nur der Teil des Lichts, der durch Materie absorbiert wird, eine Wirkung hervorruft. Entsprechend lässt sich das Reaktionsverhalten einer chemischen Verbindung steuern, wenn ihr Absorptionsverhalten der Emission der Lichtquelle angepasst wird. Eine chemische Verbindung mit einem Chromophor, der nur bei einer niedrigen Wellenlänge Licht absorbiert, wird durch langwellige Strahlung nicht angeregt. Gelingt es durch eine reversible chemische Modifikation, die photophysikalischen Eigenschaften des Chromophors zu verändern, kann man selektiv diese modifizierte Spezies anregen. Diese Chromophoraktivierung wird in α,β‐ungesättigten Carbonylverbindungen durch Lewis‐Säuren, Brønsted‐Säuren oder die Bildung von Iminiumionen hervorgerufen und kann dazu genutzt werden, Photoreaktionen bei vorgegebener Wellenlänge zu katalysieren. In diesem Kurzaufsatz wird das Konzept der Chromophoraktivierung vorgestellt, und es werden konkrete Anwendungen in der enantioselektiven Katalyse besprochen.

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Heteroatom directed photoarylation. Synthetic potential of the heteroatom oxygen

Cited by 59 publications

References 7 publications

Visible Light Photocatalysis of 6π Heterocyclization

Visible Light Photocatalysis of 6π Heterocyclization

Chromophore Activation of α,β‐Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions

Chromophoraktivierung von α,β‐ungesättigten Carbonylverbindungen und ihre Anwendung in enantioselektiven Photoreaktionen

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