Carbonylation alkyne derivatives

Ihmels H, Otto D (2005) Intercalation of Organic Dye Molecules into Double-Stranded DNA - General Principles and Recent Developments. 258 161-204 Iida H, Krische MJ (2007) Catalytic Reductive Coupling of Alkenes and Alkynes to Carbonyl Compounds and Imines Mediated by Hydrogen. 279 77-104 Imai H (2007) Self-Organized Formation of Hierarchical Structures. 270 43-72 Indelli MT, see Chiorboli C (2005) 257 63-102 Inoue Y, see Borovkov VV (2006) 265 89-146 Ishii A, Nakayama J (2005) Carbodithioic Acid Esters. 251 181-225 Ishii A, Nakayama J (2005) Carboselenothioic and Carbodiselenoic Acid Derivatives and Related Compounds. 251 227-246... 

Compounds Derived from Alkynes and Carbonyl Complexes of Cobalt, 12, 323... 

Isosydnones (146) react with alkynes to give pyrazoles (150). For example, 4,5-diphenylisosydnone (146, R1 = R2 = Ph) and ethyl phenyl propiolate gives 4-ethoxycarbonyl-l,3,5-triphenylpyrazole (150, R1 = R2 = R4 = Ph, R3 = C02Et) identical with the product from 4,5-diphenylsydnone (1, R1 = R2 = Ph).104 The rate of 1,3-cycloaddition for isosydnones (146) is relatively slow in comparison with sydnones (I) 2o,io4 a number of other cycloaddition reactions of isosydnones with alkenes, alkynes, and carbonyl compounds have been reported.20 The first isosydnone to be prepared105 was the bicyclic derivative... 

Chiral Metal Atoms in Optically Active Organo-Transition-Metal Compounds, 18, 151 13C NMR Chemical Shifts and Coupling Constants of Organometallic Compounds, 12, 135 Compounds Derived from Alkynes and Carbonyl Complexes of Cobalt, 12, 323 Conjugate Addition of Grignard Reagents to Aromatic Systems, I, 221 Coordination of Unsaturated Molecules to Transition Metals, 14, 33 Cyclobutadiene Metal Complexes, 4, 95 Cyclopentadienyl Metal Compounds, 2, 365... 

Pauson-Khand cyclization of vic-enyne derivatives of /3-lactams gave good yields of fused tricyclic compounds. The 1,4-disubstituted 2-azetidinone 391 and cobalt octacarbonyl gave the alkyne-cobalt carbonyl complex, which on thermolysis gave the tricycle 392 in 95% yield (Equation 54). When the complexes of 393 with cobalt octacarbonyl were treated with TMANO, a lower yield (65%) of 394 was obtained (Equation 55). A single diastereoisomer was formed in each case <1996TL6901>. 

Alt has prepared a cationic cis-carbene alkyne derivative, CpW(CO)-(HC=CH)[C(OEt)Me] + (77), but the presence of both an alkyne ligand and a carbonyl ligand in the d4 coordination sphere as well as a heteroatom on the carbene complicates orientational predictions relative to W(CHPh)-(RC=CR)L2X2. No structural data are yet available for this cationic carbene alkyne complex. 

No reaction was observed with internal alkynes, and carbonyl alkyne analogs undergo rapid alkyne substitution at much lower temperatures as mentioned above. Only these olefin alkyne derivatives are known to pro-... 

Fischer s carbyne complexes are thermally labile (facile loss of CO) and decompose bimolecularly with formation of alkynes. This carbonyl lability may be traced to the strong Tt-acidity of the carbyne ligand, which compromises retrodonation to the carbonyl ligands. On treatment with donor ligands, however, thermally stable substituted derivatives may be obtained (Figure 5.36). 

More recently, decarbonylation of the bridging // -alkyne complex [Rh2(//5-C5H5)2(CO)2(CF3CCCF3)] with Me3NO gave the z/2-complex, which, when treated with PF3, afforded high yields of the i 1-alkyne mixed carbonyl-trifluorophosphine derivative (8), in which the ligands are mutually trans 103). 

This article is concerned with one specific aspect of cluster organometallic chemistry, and describes the synthesis, characterization, structure, and reactivity of transition metal clusters containing alkyne, or alkyne-derived ligands. Alkynes display a diverse reactivity in their reactions with carbonyl clusters, and exhibit a wider range of coordination modes than any other simple, unsaturated molecule. It is this compelling diversity that has prompted the authors to undertake this review. 

The Pauson-Khand reaction of the 2-oxazolone-alkyne derivative, possessing an acetyl group at the triple bond terminus was not investigated, because it appeared difficult to differentiate the resulting two carbonyl functionalities (the Co-acetyl group and the C7-carbonyl moiety) of the tricyclic compound. 

In the steroid series, the alkyne cobalt carbonyl estrogen derivatives 19 and 20, substituted in position 17a and 11/3, have proved to be the most interesting. These complexes are both well recognized by ER alpha (RBA =12% and... 

Fluoroalkyl(aryl)iodonium salts are the most stable and practically important class of alkyl(aryl)iodonium derivatives. The application of such salts as electrophilic fiuoroalkylating reagents was reviewed in 1996 by Umemoto [1017]. Perfluoroalkyl(phenyl)iodonium trifiates (FITS reagents) 764 are efficient perfluoroalky-lating reagents toward various nucleophiUe substrates, sueh as arenes, carbanions, alkynes, alkenes, carbonyl compounds, amines, phosphines and sulfides [1017]. Scheme 3.300 shows several representative examples of electrophilic perfluoroalkylations using FITS reagents. 

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