title: Synthesis of fischer-type (Alkoxy)carbene complexes using diphenylsulfonium salts with functionalized alkyl groups
abstract: A new and general method for preparing Fischer-type alkoxycarbene complexes 1 is reported. This method involves the alkylation of acylate complexes 7 with alkyldiphenylsulfonium salts 10 with a variety of functionalized alkyl groups. The alkylation of tetramethylammonium pentacarbonyl(1-oxyalkylidene)chromate(0) 7a-c, tetramethylammonium pentacarbonyl(1-oxymethylidene)molybdate(0) 7d, and pentacarbonyl(1-oxymethylidene)tungstate(0) 7e with alkyldiphenylsulfonium salts 10 proceeded smoothly under mild conditions to give the corresponding alkoxycarbene complexes 12-39 in good to high yields. Competitive alkylation of 7a with methyl-11 and isopropyldiphenylsulfonium tetrafluoroborate 40 shows a higher reactivity of the isopropyl group, suggesting the participation of an S-O sulfurane intermediate 41.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan.
authors.initials: H
authors.lastname: Matsuyama
authors.initials: T
authors.lastname: Nakamura
authors.initials: M
authors.lastname: Iyoda