American Chemical Society
om050159q_si_001.pdf (2.54 MB)

Facial Stereoselectivity in the Diels−Alder Reactions of (Arylethynyl)ethoxycarbenes of Group 6 with 1,2,3,4,5-Pentamethylcyclopenta-1,3-diene and Unusual Rearrangement of Strained Norbornadienyl Fischer Carbene Complexes of Chromium(0)

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journal contribution
posted on 2005-07-04, 00:00 authored by Miguel A. Vázquez, Leonor Reyes, René Miranda, Juventino J. García, Hugo A. Jiménez-Vázquez, Joaquín Tamariz, Francisco Delgado
A study of reactivity and facial selectivity in Diels−Alder reactions of the Fischer carbene complexes (CO)5MC(C⋮CC6H4R)OCH2CH3 (1a, M = Cr, R = H; 1b, M = Cr, R = p-OCH3; 1c, M = Cr, R = p-CH3; 2, M = W, R = H; 3, M = Mo, R = H), with 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (4) was carried out. The cycloadditions were found to be highly π-facial stereoselective, favoring the anti adduct. Among these complexes, 3 was the most reactive dienophile. The stereochemical assignment of the adducts 57 was supported by NOE measurements; structures of the anti cycloadducts 5a and 6 were established by single-crystal X-ray diffraction. A [4 + 2] cycloaddition/benzannulation/rearrangement cascade reaction was observed for the chromium carbene complexes 1ac with 4 under thermal conditions, resulting in the naphthofurandione derivatives 911.