New precursors for arylcarbenes. Photocycloelimination reactions of cyclic carbonates

Griffin, G. W.; Smith, Robert L.; Manmade, A.

doi:10.1021/jo00864a034

Cited by 17 publications

(1 citation statement)

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“…Mechanistic aspects of the photoinduced fragmentation of carbonate esters have been discussed. Thus, Griffin et al reported that carbene intermediates are formed upon irradiation of cyclic carbonate esters such as 1b , as evidenced by the interception with appropriate trapping reagents; whereas the formation of persistent primary photoproducts has not been observed [ 13 ]. In contrast, we have found that under significantly milder photochemical conditions (3 h versus 15 h), the cyclic carbonates 1a and 1b ( Scheme 1 ) generate products derived from 1,3-diradical intermediates [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

Photoreactions of cyclic sulfite esters: Evidence for diradical intermediates

White¹,

Arney²,

Ihmels³

2012

Beilstein J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

Photoreactions of cyclic sulfite esters: Evidence for diradical intermediates

White¹,

Arney²,

Ihmels³

2012

Beilstein J. Org. Chem.

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Photocyclization of Stilbenes and Related Molecules

1984

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On irradiation in solution with ultraviolet (UV) light, cis ‐stilbene undergoes reversible photocyclization to give trans ‐4a,4b‐dihydrophenanthrene, an intermediate that can be trapped oxidatively with hydrogen acceptors such as iodine, oxygen, or tetracyanoethylene to give phenanthrene in high yield. This type of photoreaction occurs with a wide range of substituted stilbenes and related molecules, including various polycyclic and heterocyclic analogs; in addition, certain systems with a single heteroatom (nitrogen, oxygen, or sulfur) in place of the central π bond undergo photocyclization, creating a new five‐membered heterocyclic ring. In some of these photocyclizing systems, the transient dihydroaromatic intermediates are trapped without added oxidants by the elimination of suitable leaving groups or by various hydrogen shifts. Photocyclization is the preferred method for the synthesis of many different polynuclear aromatic systems. The discovery and early development of stilbene photocyclization has been surveyed, and several other general reviews have appeared.

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