dc.contributor.author | Connor, Dennis Andrew. | en_US |
dc.date.accessioned | 2014-10-21T12:33:39Z | |
dc.date.available | 1994 | |
dc.date.issued | 1994 | en_US |
dc.identifier.other | AAINN93768 | en_US |
dc.identifier.uri | http://hdl.handle.net/10222/55405 | |
dc.description | The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction forms 1:1:1 adducts of nucleophiles, olefins and electron-poor aromatics. The usual aromatic and nucleophile, thus far in the exploration, are 1,4-dicyanobenzene and methanol in acetonitrile. The transformation proceeds by photoinduced electron transfer to the excited aromatic from the olefin. | en_US |
dc.description | The potential of the photo-NOCAS reaction to be a synthetic tool has driven studies of the scope and limitations to investigate the intermediate cyclizations of nonconjugated dienes. The interesting dynamics of radical cations and the 1,6-endo, endo cyclization of 2,5-dimethyl-1,5-hexadiene as the radical-cation intermediate of the photo-NOCAS reaction led to the present interest in (R)-(+)-limonene and 2,6-dimethyl-1,6-heptadiene. The photo-NOCAS products of (R)-(+)-limonene are four uncyclized regio- and stereoisomers of photo-NOCAS reaction at the endocyclic double bond. The products of 2,6-dimethyl-1,6-heptadiene are an acyclic photo-NOCAS product, two cyclohexanes (cis and trans) and two cycloheptanes (cis and trans). The cycloheptanes are the products of a 1,7-endo, endo radical-cation cyclization. The cyclohexanes are the results of 1,6-endo cyclization of the intermediate $\beta$-methoxy radical. | en_US |
dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 1994. | en_US |
dc.language | eng | en_US |
dc.publisher | Dalhousie University | en_US |
dc.publisher | | en_US |
dc.subject | Chemistry, Organic. | en_US |
dc.title | The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reactions of (R)-(+)-limonene and 2,6-dimethyl-1,6-heptadiene. | en_US |
dc.type | text | en_US |
dc.contributor.degree | Ph.D. | en_US |