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Carbenes stabilised

Non-heteroatom-stabilised Fischer carbene complexes also react with alkenes to give mixtures of olefin metathesis products and cyclopropane derivatives which are frequently the minor reaction products [19]. Furthermore, non-heteroatom-stabilised vinylcarbene complexes, generated in situ by reaction of an alkoxy- or aminocarbene complex with an alkyne, are able to react with different types of alkenes in an intramolecular or intermolecular process to produce bicyclic compounds containing a cyclopropane ring [20]. [Pg.65]

Catalytic cyclopropanation of alkenes has been reported by the use of diazoalkanes and electron-rich olefins in the presence of catalytic amounts of pentacarbonyl(rj2-ris-cyclooctene)chromium [23a,b] (Scheme 6) and by treatment of conjugated ene-yne ketone derivatives with different alkyl- and donor-substituted alkenes in the presence of a catalytic amount of pentacarbon-ylchromium tetrahydrofuran complex [23c]. These [2S+1C] cycloaddition reactions catalysed by a Cr(0) complex proceed at room temperature and involve the formation of a non-heteroatom-stabilised carbene complex as intermediate. [Pg.66]

Simple 1,3-dienes also undergo a thermal monocyclopropanation reaction with methoxy(alkyl)- and methoxy(aryl)carbene complexes of molybdenum and chromium [27]. The most complete study was carried out by Harvey and Lund and they showed that this process occurs with high levels of both regio-and diastereoselectivity. The chemical yield is significantly higher with molybdenum complexes [27a] (Scheme 7). Tri- and tetrasubstituted 1,3-dienes and 3-methylenecyclohexene (diene locked in an s-trans conformation) fail to react [28]. The monocyclopropanation of electronically neutral 1,3-dienes with non-heteroatom-stabilised carbene complexes has also been described [29]. [Pg.67]

At this point the catalytic process developed by Dotz et al. using diazoalkanes and electron-rich dienes in the presence of catalytic amounts of pentacar-bonyl(r]2-ds-cyclooctene)chromium should be mentioned. This reaction leads to cyclopentene derivatives in a process which can be considered as a formal [4S+1C] cycloaddition reaction. A Fischer-type non-heteroatom-stabilised chromium carbene complex has been observed as an intermediate in this reaction [23a]. [Pg.88]

Alkynylcarbene complexes react with strained and hindered olefins yielding products that incorporate up to four different components by the formation of five new carbon-carbon bonds [15b]. This remarkable transformation is explained by an initial [2+2] cycloaddition followed by CO insertion. The resulting intermediate suffers a well precedented [1,3]-migration of the metal fragment to generate a non-heteroatom-stabilised carbene complex intermediate which reacts with a new molecule of the olefin through a cyclopropana-tion reaction (Scheme 85). [Pg.115]

The electrophilic carbene carbon atom of Fischer carbene complexes is usually stabilised through 7i-donation of an alkoxy or amino substituent. This type of electronic stabilisation renders carbene complexes thermostable nevertheless, they have to be stored and handled under inert gas in order to avoid oxidative decomposition. In a typical benzannulation protocol, the carbene complex is reacted with a 10% excess of the alkyne at a temperature between 45 and 60 °C in an ethereal solvent. On the other hand, the non-stabilised and highly electrophilic diphenylcarbene pentacarbonylchromium complex needs to be stored and handled at temperatures below -20 °C, which allows one to carry out benzannulation reactions at room temperature [34]. Recently, the first syntheses of tricyclic carbene complexes derived from diazo precursors have been performed and applied to benzannulation [35a,b]. The reaction of the non-planar dibenzocycloheptenylidene complex 28 with 1-hexyne afforded the Cr(CO)3-coordinated tetracyclic benzannulation product 29 in a completely regio- and diastereoselective way [35c] (Scheme 18). [Pg.134]

A benzannulation reaction yielding the naphthoquinone 61 could also be performed with the ruthenium carborane-stabilised carbene 60 and 1-hexyne [56] (Scheme 36). The ruthenium carbene unit can be regarded as an 18-electron fragment containing a formal Ru(II) centre coordinated to a dianionic six-electron-donor cobaltacarborane ligand. [Pg.142]

A60. J. P. Candlin, K. A. Taylor, and D. T. Thompson, "Reactions of Transition-Metal Complexes. Elsevier, Amsterdam, 1968. A review of types of reactions of metal complexes (e.g., substitution, combination, redox) reactions with various reagents (e.g., hydrocarbons, halides, carbon monoxide, and isonitrile) and preparation of new stabilised organic systems (e.g., metallocenes, carbenes). Intended for research workers, consequently written at a fairly high level, with emphasis on organometallics. A61. H. J. Keller, NMR-Untersuchungen an Komplexverbindungen. Springer, Berlin, 1970. Expansion of review article 37.1. [Pg.448]

There have been ab initio studies of the bonding for a series of imino and amino phosphorus molecules,15 and for the phosphonium ylides (8).14 The anion character of the ylidic carbon is intermediate between that of olefinic and substituted carbanions. Polarisation of the H3P group has a stabilising effect. The influence of the substituent X on the inversion of the carbanion and also the tendency of the molecule to dissociate to carbene and phosphine is also discussed.14 CNDO/S MO calculations on the... [Pg.395]

However, difluoromethylation occurs when nucleophiles intercept difluoro-carbene generated under basic conditions, providing a route to difluoromethyl-ethers of phenols [33] and thiophenols [34]. The reaction with phosphite anion leads to the corresponding difluoromethyl phosphonate (see Sect. 2.3.2) while nucleophilic carbanions such as alkynes [35] also undergo formal alkylation, as do malonates [36,37]. An -difluoromethylaziridine was reported in a reaction with a glycine imine [38]. The scope of the established chemistry is summarised in Fig. 1. Bromodifluoromethylation occurs with a similar range of nucleophiles [39,40], and also with carbonyl-stabilised carbanions such as malonates [41,42]. [Pg.137]

As mentioned above, the electrophilic metal carbene complexes are stabilised by the presence of heteroatoms or phenyl rings at the divalent carbon atom, while hydrogen or alkyl groups stabilise the nucleophilic complexes. Therefore, there is a distinction between carbenoids and alkylidenes when designing carbene ligands corresponding to the former or the latter class. [Pg.345]

The third example is valuable particularly because of the ready availability of chlorocyclopropylsulfides such as 19 by reaction of a sulfide-stabilised carbene with an alkene. [Pg.114]

Overall, the transformations are equivalent to carbene additions to the styrenes. However, a carbene mechanism can be ruled out since the only alkenes which are successful are those carrying anion-stabilising groups. [Pg.292]

In practice, donor substituents make it possible actually to isolate a range of carbenes 4.105. With somewhat less stabilisation, the carbene 4.106, although it is only found as a reactive intermediate, is exceptionally easy to form. It is the key intermediate in all the metabolic steps catalysed by thiamine coenzymes, and its reactions are characterised by its nucleophilicity. Similarly, dimethoxycarbene 4.107 reacts as a nucleophile with electrophiles like dimethyl maleate to give the intermediate 4.108, and hence the cyclopropane 4.109, but it does not insert into unactivated alkenes. [Pg.148]

The combined features of charge and catalyst stabilisation find their expression in markedly enhanced recyclability. Using catalyst loadings of 2.5 - 5 mol%, the activity decreased by only a few percent after 10 cycles and remained above 90% of the initial value. Furthermore, the catalyst solution could be kept for months without measurable loss in activity. By substituting the tricyclohexylphosphine ligand for a A -heterocyclic carbene, catalyst stability was further improved which finds its expression in very low residual ruthenium levels in the isolated product.[44] As these are only the... [Pg.162]

Methylbenzoate was obtained from iodobenzene in moderate to good yield with polymer-stabilised palladium nanoparticles as the catalyst.1391 Of the ionic liquids screened in the reaction, those based on the pyridinium cation generally gave better results than imidazolium-type liquids. The latter probably deactivate the catalyst by formation of stable carbene complexes. [Pg.194]


See other pages where Carbenes stabilised is mentioned: [Pg.17]    [Pg.30]    [Pg.24]    [Pg.27]    [Pg.29]    [Pg.30]    [Pg.17]    [Pg.30]    [Pg.24]    [Pg.27]    [Pg.29]    [Pg.30]    [Pg.60]    [Pg.61]    [Pg.91]    [Pg.111]    [Pg.54]    [Pg.84]    [Pg.163]    [Pg.237]    [Pg.430]    [Pg.182]    [Pg.360]    [Pg.344]    [Pg.232]    [Pg.271]    [Pg.126]    [Pg.345]    [Pg.140]    [Pg.95]    [Pg.5]    [Pg.29]    [Pg.41]    [Pg.46]    [Pg.166]    [Pg.122]    [Pg.172]   
See also in sourсe #XX -- [ Pg.148 ]

See also in sourсe #XX -- [ Pg.199 , Pg.202 ]




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Stabilisation Stabilise

Stabilisation Stabilised

Stabilisation Stabiliser

Stabilisation stabilisates

Stabilise

Stabilisers

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