Photochemical Preparation of Highly Functionalized 1-Indanones Export

@article{Wessig2004, abstract = {Abstract: A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements.}, address = {Institut f\"{u}r Chemie, Humboldt-Universit\"{a}t zu Berlin, D-12489 Berlin, Germany}, author = {Wessig, P. and Glombitza, C. and Muller, G. and Teubner, J.}, citeulike-article-id = {3446267}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/jo040173x}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/jo040173x}, day = {29}, doi = {10.1021/jo040173x}, journal = {J. Org. Chem.}, keywords = {diplom, indanon, norrish, photochemistry, shift, spincenter, young}, month = {October}, number = {22}, pages = {7582--7591}, posted-at = {2008-10-24 09:55:54}, priority = {0}, title = {Photochemical Preparation of Highly Functionalized 1-Indanones}, url = {http://dx.doi.org/10.1021/jo040173x}, volume = {69}, year = {2004} }

TY - JOUR ID - Wessig2004 L3 - citeulike-article-id:3446267 N2 - Abstract: A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements. IS - 22 JF - J. Org. Chem. AD - Institut für Chemie, Humboldt-Universität zu Berlin, D-12489 Berlin, Germany EP - 7591 TI - Photochemical Preparation of Highly Functionalized 1-Indanones VL - 69 SP - 7582 KW - diplom KW - indanon KW - norrish KW - photochemistry KW - shift KW - spincenter KW - young AU - Wessig, P AU - Glombitza, C AU - Muller, G AU - Teubner, J PY - 2004/10/29/ UR - http://dx.doi.org/10.1021/jo040173x ER -