Cyclization Reactions of Aryl Propargyl Acetates with Tethered Epoxide Induced by Ruthenium Complex.

Reactions of the ruthenium complex [Ru]Cl ([Ru]=Cp(PPh3 )2 Ru; Cp=η5 -C5 H5 ) with several aryl propargyl acetates, each with an ortho-substituted chain of various length containing an epoxide on the aromatic ring and with or without methyl substitutents on the epoxide ring, bring about novel cyclizations. The cyclization reactions of HC≡CCH(OAc)(C6 H4 )CH2 (RC2 H2 O) (R=H, 6 a; R=CH3 , 6 b, where RC2 H2 O is an epoxide ring) in MeOH give the vinylidene complexes 5 a-b, respectively, each with the Cß integrated into a tetrahydro-5H-benzo[7]annulen-6-ol ring. A C-C bond formation takes place between the propargyl acetate and the less substituted carbon of the epoxide ring. Further cyclizations of 5 a-b induced by HBF4 give the corresponding vinylidene complexes 8 a-b each with a new 8-oxabicyclo-[3.2.1]octane ring by removal of a methanol molecule in high yield. For similar aryl propargyl acetates with a shorter epoxide chain, the cyclization gives a mixture of a vinylidene complex with a tetrahydronaphthalen-1-ol ring and a carbene complex with a tricyclic indeno-furan ring. For the cyclization of 18, with a longer epoxide chain, opening of the epoxide is required to afford the vicinal bromohydrin 22, then tandem cyclization occurs in one pot. Products are characterized by spectroscopic methods as well as by XRD analysis.

Reactions of aromatic S- and O-enynes with two methyl substituents on the olefinic unit assisted by a ruthenium complex: tandem cyclization and product selectivity.

Ruthenium-assisted cyclizations of two enynes, HC≡CCH(OH)(C6H4)X-CH2CH=CMe2 (X=S (1a), O (1b)), each of which contains two terminal methyl substituents on the olefinic parts, are explored. The reaction of 1a in CH2Cl2 gives the vinylidene complex 2a from the first cyclization and two side products, 3a and the carbene complex 4a with a benzothiophene ligand. The same reaction in the presence of HBF4 affords 4a exclusively. Air oxidation of 4a in the presence of Et3N readily gives an aldehyde product. In MeOH, tandem cyclizations of 1a generate a mixture of the benzothiochromene compound 10a and the carbene complex 7a also with a benzothiochromene ligand. First, cyclization of 1b likewise proceeds in CH2Cl2 to give 2b. Tandem cyclization of 1b in MeOH yields comparable products 10b and 7b with benzochromene moieties, yet with no other side product. The reaction of [Ru]Cl with HC≡CCH(OH)(C6H4)S-CH2CH=CH2 (1c), which contains no methyl substituent in the olefinic part, in MeOH gives the carbene complex 15c with an unsubstituted thiochromene by means of a C-S bond formation. Structures of 3a and 15c are confirmed by X-ray diffraction analysis. The presence of methyl groups of enynes 1a and 1b promotes sequential cyclization reactions that involve C-C bond formation through carbocationic species.