Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Carbene insertion reactions, group 4 metal

A similar type of chiral rhodium porphyrin was found to be effective for the carbene-insertion reaction to olefins, where formation of the carbene complex takes place. Chiral rhodium complexes for catalytic stereoselective-carbene addition to olefins were prepared by condensation of a chiral aldehyde and pyrrole. Formation of the metal-carbene complex and substrate access to the catalytic center are crucial to the production of optically active cyclopropane derivatives. Optically active a-methoxy-a-(trifluoro-methyOphenylacetyl groups are linked witfi the amino groups of a,p,0L,p isomers of tetrakis-(2-aminophenyI)por-phyrin through amide bonds. Oxidation reactions of the... [Pg.285]

Abstract The photoinduced reactions of metal carbene complexes, particularly Group 6 Fischer carbenes, are comprehensively presented in this chapter with a complete listing of published examples. A majority of these processes involve CO insertion to produce species that have ketene-like reactivity. Cyclo addition reactions presented include reaction with imines to form /1-lactams, with alkenes to form cyclobutanones, with aldehydes to form /1-lactones, and with azoarenes to form diazetidinones. Photoinduced benzannulation processes are included. Reactions involving nucleophilic attack to form esters, amino acids, peptides, allenes, acylated arenes, and aza-Cope rearrangement products are detailed. A number of photoinduced reactions of carbenes do not involve CO insertion. These include reactions with sulfur ylides and sulfilimines, cyclopropanation, 1,3-dipolar cycloadditions, and acyl migrations. [Pg.157]

For comparison, let us also consider the experimentally well-documented51 singlet reactions of H2 with group 9 metal carbene cations to give metal dihydride insertion products, e.g., for M = Ir,... [Pg.495]

As shown in the previous two sections, rhodium(n) dimers are superior catalysts for metal carbene C-H insertion reactions. For nitrene C-H insertion reactions, many catalysts found to be effective for carbene transfer are also effective for these reactions. Particularly, Rh2(OAc)4 has demonstrated great effectiveness in the inter- and intramolecular nitrene C-H insertions. The exploration of enantioselective C-H amination using chiral rhodium catalysts has been reported by several groups.225,244,253-255 Hashimoto s dirhodium tetrakis[A-tetrachlorophthaloyl-(A)-/ r/-leuci-nate], Rh2(derived rhodium complex, Rh2(i -BNP)4 48,244 afforded moderate enantiomeric excess for amidation of benzylic C-H bonds with NsN=IPh. [Pg.196]

The pincer like diamino functionalised carbene ligand stabilises the group 4 metal sufficiently to perform a few very interesting insertion reactions with the M-Me bond. The reactions were performed with the hafnium rather than the zirconium complexes [113]. Small molecules used for these insertion reactions include isonitriles (aryl and alkyl) and CO (see Figure 4.36). Reaction of the hafnium carbene dimethyl complex with xylyl-isonitrile results in addition of this excellent donor ligand and subsequent insertion into the Hf-Me... [Pg.227]

Intermolecular reactions between coordinatively unsaturated metal atoms and the C-H groups of relatively unreactive hydrocarbons such as cyclohexane and even methane have been reported (Scheme 1.4). ° Insertion reactions of carbenes R R C into C-H or other bonds are clearly of the same type, the carbene carbon atom playing the role of the coordinatively unsaturated metal... [Pg.31]

It might be interesting to note that the proponents of the carbene mechanism (mentioned earlier), point out that this is also consistent with their mechanism [254, 255], The reaction can consist of (a) an insertion of a metal into an a-CH bond of a metal alkyl to form a metal-carbene hydride complex. This is followed by (b) reaction of the metal-carbene unit with an alkene to form a metal-cyclobutane-hydride intermediate. The final step (c), is a reductive elimination of hydride and alkyl groups to produce a chain-lengthened metal alkyls. This assures that a chiral metal environment is maintained [254]. It is generally believed [258], however, that stereospecific propagation comes from concerted, multicentered reactions, as was shown in the Cossee-Arlman mechanism. The initiator is coordinated... [Pg.206]

In addition to their thermodynamic propensity to dimerize [16], free acyclic car-benes containing alkyl groups are prone to decomposition via intramolecular C—H insertion reactions that lead to net elimination of an alkene (Scheme 16.3a) [35]. Loss of two alkene equivalents has been observed to occur from an Alder-type ADC bound to W or Mo tetracarbonyl fragments, resulting in conversion to an amidine ligand (Scheme 16.3b) [36]. This process appears to be limited to zerovalent metal complexes and may be facihtated by the unusual -(C,N) binding mode of the carbene. [Pg.528]

Diazo compounds, with or without metal catalysis, are well-known sources of carbenes. For synthetic purposes a metal catalyst is used. The diazo compounds employed are usually a- to an electron-withdrawing group, such as an ester or a ketone, for stability. In the early days, copper powder was the catalyst of choice, but now salts of rhodium are favoured. The chemistry that results looks very like the chemistry of free carbenes, involving cyclopropanation of alkenes, cyclopropenation of alkynes, C-H insertion reactions and nucleophilic trapping. As with other reactions in this chapter, free carbenes are not involved. Rhodium-carbene complexes are responsible for the chemistry. This has enormous consequences for the synthetic applications of the carbenes - not only does the metal tame the ferocity of the carbene, but it also allows control of the chemo-, regio- and stereoselectivity of the reaction by the choice of ligands. [Pg.312]


See other pages where Carbene insertion reactions, group 4 metal is mentioned: [Pg.34]    [Pg.293]    [Pg.359]    [Pg.204]    [Pg.267]    [Pg.151]    [Pg.233]    [Pg.257]    [Pg.3225]    [Pg.3954]    [Pg.496]    [Pg.458]    [Pg.628]    [Pg.236]    [Pg.315]    [Pg.28]    [Pg.140]    [Pg.102]    [Pg.3224]    [Pg.3953]    [Pg.124]    [Pg.125]    [Pg.2]    [Pg.35]    [Pg.423]    [Pg.99]    [Pg.864]    [Pg.864]    [Pg.867]    [Pg.195]    [Pg.222]    [Pg.301]    [Pg.554]    [Pg.98]    [Pg.190]    [Pg.218]    [Pg.554]   


SEARCH



Carbene group

Carbene insertion

Carbene insertion reaction

Carbene insertion reactions carbenes

Carbene insertion reactions, group 4 metal direction

Carbene reactions

Carbenes insertion

Carbenes reactions

Group 4 metal substituents carbene insertion reactions

Insertion reactions

Insertion, group

Metal carbenes

Metal groups reactions

Metal insertion

Metal insertion reactions

Metal inserts

© 2024 chempedia.info