The arene–alkene photocycloaddition

Streit, Ursula; Bochet, Christian G.

doi:10.3762/bjoc.7.61

Cited by 88 publications

(90 citation statements)

References 99 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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.…”

mentioning

confidence: 99%

See 1 more Smart Citation

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

2016

View full text Add to dashboard Cite

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.

show abstract

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

View full text Add to dashboard Cite

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

The arene–alkene photocycloaddition

Cited by 88 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

Contact Info

Product

Resources

About