Preparation of Fischer carbene complexes by alkylation of acylmetalates with alkyl iodides
作者:Thomas R. Hoye、Kejian Chen、James R. Vyvyan
DOI:10.1021/om00031a056
日期:1993.7
Neutral Fischer carbene complexes bearing alkoxy groups as the donor substituents on the carbene carbon atom have been synthesized by direct alkylation of the lithium acylmetalates (formed by classical addition of organolithium compounds to metal hexacarbonyl) by alkyl iodides. It was shown that the reaction proceeds under normal phase-transfer conditions (CH2-Cl2/H2O) or, preferably, in aqueous medium alone. However, in both cases the presence of a catalytic amount of a tetraalkylammonium salt (n-Bu4NBr) was required. Attractive features of this methodology are (i) the economy of using alkyl iodides in place of the usual alkylating agents (like Me3O+BF4-, magic methyl, or methyl triflate), (ii) the procedural ease of ''one-pot'' preparation of the carbene complexes, and (iii) the greater variety of alkyl moieties that can be incorporated as part of the alkoxy substituent using the more readily available alkyl iodides containing nontrivial alkyl groups. The procedure is preparatively useful for accessing chromium-containing carbenes, but yields of the analogous molybdenum- and tungsten-containing species are only less-than-or-equal-to 10%. Mechanistic considerations suggest that products are formed by competing pathways involving direct S(N)2 displacement vs electron-transfer-initiated S(RN)1 processes.
New Method for the Preparation of Alkoxycarbene Complexes of Chromium, Molybdenum, and Tungsten Using Sulfonium Salts
作者:Takako Nakamura、Haruo Matsuyama、Masahiko Iyoda
DOI:10.1246/cl.1994.1537
日期:1994.8
Alkylation of tetramethylammonium acylate complexes of chromium, molybdenum, and tungsten with alkyldiphenylsulfonium salts readily proceeds under mild conditions to afford alkoxycarbene complexes containing a variety of functional groups in good yields.