Masamichi Maruta

ASYMMETRIC CATALYSIS OF CARBONYL-ENE AND ALDOL REACTIONS WITH FLUORAL BY CHIRAL BINAPHTHOL-DERIVED TITANIUM COMPLEX

Abstract The chiral titanium complex-catalyzed ene-type reaction and the Mukaiyama aldol reaction with fluoral are shown to serve as an efficient route to the enantioselective and diastercoselective synthesis of CF 3 -substituted components of biological and synthetic importance.

Diastereoselective and enantioselective catalysis of the carbonyl-ene reaction with fluoral

Abstract The chiral titanium complex-catalyzed carbonyl-ene reaction with fluoral is shown to serve as an efficient route for the syn-diastereoselective and enantioselective synthesis of CF3-substituted compounds of biological and synthetic importance.

Fluorine-containing seven-membered benzoheterocycles derived from hexafluoropropene oligomers

Abstract 4-Fluoro-2-( F -ethyl)-3-( F -methyl)-1, 5-benzoxazepine was prepared by reaction of F -2-methyl-2-pentene with 2-aminophenol in the presence of triethylamine in diethyl ether. The reaction of F -2,4-dimethyl-3-heptene with 2-aminophenol in dimethylformamide gave 7-( F -1-methylethyl)-8- ( F -ethyl)-9,14-benzoxazepino[4,3-b]1,6-benzoxazepine. Several ortho-bifunctional benzenes reacted similarly with F -2-methyl-2-pentene and F -2,4-dimethyl-3-heptene to give the corresponding seven-membered benzoheterocycles.

Trifluoromethylcyclohexane as a new solvent? Limits of use

Abstract Reactivity and stability of trifluoromethylcyclohexane (TFMC) has been investigated towards various reagents, in order to evaluate its possible use as solvent. TFMC is stable in most oxidizing conditions, indicating the protective effect of a fluoroalkyl substituent towards oxidation, and surprisingly, it is also very stable towards strong bases. TFMC has also been assessed as a chlorinated solvent substitute in some reactions. It is clearly adapted as a CCl 4 substitute in allylic bromination reaction.

Some unusual reactions of dimers of F-propene with thiols

Abstract Reactions of F -2- and -4-methly-2-pentenes with thiols were found to involve an oxidation-reduction system. 1,4-Elimination of sulfenyl fluorides from thio-substituted perfluoroolefins to form 1,3-dienes and disulfides is suggested as the reaction pathway.

Mode of the nucleophilic reaction of F-2,4-dimethyl-3-heptene and phenol

Abstract Nucleophilic substitution on F -2,4-dimethyl-3-heptene (3) by sodium phenoxide in diethyl ether gave 3-phenoxylated F -2,4-dimethyl-4- (5) and -3-heptenes (6). In contrast, the reaction of (3) with phenol and triethylamine in dimethylformamide afforded 4-phenoxylated F -2,4-dimethyl-3-heptene (7) as the major product. The reaction mechanisms are discussed.