The arene–alkene photocycloaddition

Streit, Ursula; Bochet, Christian G.

doi:10.3762/bjoc.7.61

Cited by 91 publications

(90 citation statements)

References 99 publications

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“…An optimization study showed that a ketone in the 2-position of the pyrrole was essential to enable lactam formation (Table 3, entries [1][2][3][4][5] and that a second ketone was actually deleterious to the process (entry 6). Although yields averaged around 50%, this in itself is quite remarkable as intense, high energy 254 nm UV light is used and the successful formation of 22 relies on 3-successive and independent photon mediated events.…”

Section: Scheme 4 Mechanism Of Tricyclic Imine Formationmentioning

confidence: 99%

“…Part of this is due to reaction types specific to the photochemical excited state such as alkene-alkene [2+2], 1 arene metaphotocycloaddition, 2 di-π-methine rearrangements 3 and various Norrish-Yang 4 type hydrogen abstraction-recombination sequences to name but a few. Useful sequences involving a second photon mediated step are rare, 5 but do offer the promise of large increases in molecular complexity due to massive reorganization of the original starting material structure.…”

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confidence: 99%

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Conformationally Driven Two- and Three-Photon Cascade Processes in the Stereoselective Photorearrangement of Pyrroles

2016

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms Conformationally Driven 2-and 3-Photon Cascade Processes in the Stereoselective Photorearrangement of PyrrolesPaul J. Koovits, Jonathan P. Knowles, Kevin I. Booker-Milburn* School of Chemistry, University of Bristol, Cantock's Close, Bristol, UK, BS8 1TS Supporting Information Placeholder ABSTRACT: A TBSO group has been shown to exert a high degree of stereocontrol during the 2-photon photocycloaddition/rearrangement of N-butenyl pyrroles to complex tricyclic aziridines. Moreover this and other bulky groups have been shown to change the outcome of the reaction, promoting a new 2-photon sequence to tricyclic imines and an unprecedented stereoselective 3-photon sequence to azabicyclo[3.3.1]nonanes.

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Section: Scheme 4 Mechanism Of Tricyclic Imine Formationmentioning

confidence: 99%

mentioning

confidence: 99%

Conformationally Driven Two- and Three-Photon Cascade Processes in the Stereoselective Photorearrangement of Pyrroles

2016

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“…1,2 In the presence of alkenes photocycloaddition can result, leading to ortho, meta, and para adducts, for example, [2+2], [3+2] and [4+2] cycloadditions, Figure 1. meta-Cycloaddition of alkenes with benzene has been extensively exploited to construct a dazzling array of synthetic targets, [3][4][5] while ortho and para cycloadditions of benzene have received less attention. 5,6 Higherorder cycloadditions of benzene are even more rare.…”

Section: Introductionmentioning

confidence: 99%

Photo-[4+4]-cycloaddition (para) of meta-substituted benzenes with 2-pyridones

Khatri

Vrubliauskas

Sieburth

2015

Tetrahedron Letters

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a b s t r a c tBenzene is unreactive as a photochemistry partner with 2-pyridone, however benzene substitution can allow for an efficient [4+4] (a k a, 'para') photocycloaddition. Productive substituents include alkoxy, cyano, ester, and trifluoromethyl, suggesting that inductively electron-withdrawing groups are sufficient, however a single fluorine substituent does not result in cycloaddition. When the product of this cycloaddition contains a conjugated system (e.g., an unsaturated ester) a secondary photocycloaddition can follow, forming triply bridged all-syn-[3]ladderane products.

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“…These reactions are "atomeconomical" and "step-economical"; all the atoms in the reactants appear in the products and complexity can be achieved in a single step [1,2]. With unprecedented possibilities to efficiently create various new molecules, photocycloadditions are widely applied in organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

Effect of Initial Orientation on the Laser-Induced Cycloaddition Reaction of Benzene and Ethylene

Yuan

Hong

Wang

et al. 2014

International Journal of Photoenergy

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The [2 + 2] photocycloaddition reaction of benzene and ethylene was investigated by semiclassical dynamics simulation and complete active space self-consistent field (CASSCF) ab initio calculations. Following laser excitation of the benzene molecule, two mechanisms were observed depending on the location of the second C of ethylene in relation to the hexagonal prism space defined by the first C and the plane of the benzene ring. Synchronous formation of two bonds was observed when the second C is outside the prism space; an asynchronous mechanism is observed otherwise. Charge transfer was observed only in the asynchronous mechanism; CASSCF calculations suggest that the asynchronous mechanism involves a barrierless path from the Frank-Condon point to a conical intersection, while the synchronous mechanism involves 0.8 eV barrier. These results are consistent with a higher quantum yield observed in the simulations for the asynchronous pathway.

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The arene–alkene photocycloaddition

Cited by 91 publications

References 99 publications

Conformationally Driven Two- and Three-Photon Cascade Processes in the Stereoselective Photorearrangement of Pyrroles

Conformationally Driven Two- and Three-Photon Cascade Processes in the Stereoselective Photorearrangement of Pyrroles

Photo-[4+4]-cycloaddition (para) of meta-substituted benzenes with 2-pyridones

Effect of Initial Orientation on the Laser-Induced Cycloaddition Reaction of Benzene and Ethylene

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