ChemInform Abstract: Synthesis of New Polycyclic Oxazol-2-one Derivatives by a Tandem [4 + 2] Cycloaddition/Cyclopentannulation/1,5-Sigmatropic Rearrangement Process of Fischer (Arylalkynyl)(alkoxy)carbenes and exo-2-Oxazolidinone Dienes

An efficient and simple synthesis of highly substituted 9-ethoxy-3-phenyl-3H-fluorene[3,2-d]oxazol-2-(4H,9H,10H)-one derivatives 10a−f by a tandem [4 + 2] cycloaddition/cyclopentannulation process of Fischer (arylethynyl)(ethoxy)carbene complexes (CO)5M═C(C≡CC6H4-R)OCH2CH3 (1a, M = Cr, R = H; 1b, M = Cr, R = p-CH3; 1c, M = Cr, R = p-OCH3; 1d, M = W, R = H; 1e, M = W, R = p-CH3; 1f, M = W, R = p-OCH3) with exo-2-oxazolidinone dienes 7a−d is described. A study of reactivity as well as regio- and stereoselectivity in a tandem process of the Fischer carbene complexes 1 with the exo-heterocyclic dienes 7 was carried out. The cycloadditions were found to be highly regioselective, favoring the para cycloadducts, and highly stereoselective, giving the trans diastereoisomers. The stereochemical assignment of the cycloadducts was supported by NOE measurements, and the derivatives 10b,c,e were further characterized by single crystal X-ray diffraction. A rationalization of the regioselectivity was carried out through...