- Synthesis of Fischer-Type (Alkoxy)carbene Complexes Using Diphenylsulfonium Salts with Functionalized Alkyl Groups
-
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.
- Matsuyama, Haruo,Nakamura, Takako,Iyoda, Masahiko
-
-
Read Online
- Syntheses, structures, and reactivities of two chalcogen-stabilized carbones
-
Electronic effects on the central carbon atom of carbone, generated by the replacement of the SIV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph2E, E=S or Se), were investigated. The carbones Ph2E→C←SPh2(NMe) [E=S(1) or Se(2)] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2, which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2>1>CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four-electron donor. Carbodichalcogenuranes: New carbones of the type Ph2E→C← SPh2(NMe) [E=S (1) or Se (2)] were synthesized and characterized. The carbone 2 can be used to generate a doubly protonated dication and a C-metalated trication with silver(I) and thus provide the first experimental proof of carbodichalcogenurane behaving as a four-electron donor ligand.
- Morosaki, Tomohito,Suzuki, Tsubasa,Wang, Wei-Wei,Nagase, Shigeru,Fujii, Takayoshi
-
-
Read Online
- Synthesis and chemistry of enantiomerically pure 10,11-dihydrodibenzo[b,f] thiepines
-
Several chiral thiepines were efficiently constructed using sulfur diimidazole in combination with a variety of bislithiated carbon fragments. The sulfur atom in these thiepines is found to be unusually unreactive compared to diphenylsulfide. The Royal Society of Chemistry 2006.
- Wyatt, Paul,Hudson, Andrew,Charmant, Jonathan,Orpen, A. Guy,Phetmung, Hirihattaya
-
p. 2218 - 2232
(2008/02/04)
-
- The efficiency of diphenylalkylsulfonium salts as alkylating agents
-
A series of the title reagents have been used for the alkylation of a number of nucleophiles including iodide, cyanide, thiocyanate and fluoride ions as well as ethyl acetoacetate, phenylacetonitrile and a variety of nitrogen heterocyclic compounds.The results compared favorably with literature methods.
- Badet, Bernard,Julia, Marc,Lefebvre, Christian
-
p. 431 - 434
(2007/10/02)
-