Chelation intermediate complexes

The mechanism of organolithium addition to naphthyl oxazolines is believed to occur via initial complexation of the alkyllithium reagent to the oxazoline nitrogen atom and the methyl ether to form chelated intermediate 17. Addition of the alkyl group to the arena 7t-system affords azaenolate 18, which undergoes reaction with an electrophile on the opposite face of the alkyl group to provide the observed product 4. The chelating methyl... 

McLafferty rearrangement 133, 163 Meisenheimer complexes 699, 702 Metal-chelated intermediates 838 Metal-halogen exchange 781, 784 Methionine, oxidation of 852-855 Methionine sulphone 853 Methionine sulphoxide 851-869 reduction of 1063 residues of... 

First, solvent molecules, referred to as S in the catalyst precursor, are displaced by the olefinic substrate to form a chelated Rh complex in which the olefinic bond and the amide carbonyl oxygen interact with the Rh(I) center (rate constant k ). Hydrogen then oxidatively adds to the metal, forming the Rh(III) dihydride intermediate (rate constant kj). This is the rate-limiting step under normal conditions. One hydride on the metal is then transferred to the coordinated olefinic bond to form a five-membered chelated alkyl-Rh(III) intermediate (rate constant k3). Finally, reductive elimination of the product from the complex (rate constant k4) completes the catalytic cycle. 

Only with less efficient catalysts and at low temperature, have p-chelate intermediates been intercepted by P H HP NMR spectroscopy in the course of copolymerisations in MeOH-d4 [5g]. The unambiguous detection of p-chelates has been observed in a reaction catalysed by the l,r-bis(diphenylphosphino)ferro-cene complex [Pd(H20)2(dppf)](0Ts)2 (3) at room temperature (Scheme 7.7) [5g]. As shown in the sequence of P H NMR spectra reported in Figure 7.8, the P-chelate intermediates 4- disappeared already at 50 °C. A parallel model study confirmed the formation and the structure of the dppf P-chelates and also provided information of more elusive intermediates (see Section 7.2.1.8) [19]. 

The early stages in the chain growth process have been mimicked by Braunstein with the use of a Pd-Me complex supported by an acetamido-derived P-O ligand. Four catalytic intermediates were intercepted by the sequential addition of CO-ethene-CO-ethene, and the occurrence of reversible and irreversible steps was established (Scheme 7.9). Unlike diphosphine ligands [10], the insertion of ethene into the y-chelate acyl complex was found to be a facile process occurring without the intervention of CO [25]. 

Decarboxylation of carbonate complexes is usually effected by acid hydrolysis with the formation of a C02 free oxide or hydroxide complex.128 All such reactions involve a protonated (bicarbonate) intermediate but there are some useful deferences which, in many instances, may be reconciled with the three main structural types of carbonate complexes. Both unidentate and chelate carbonates readily yield C02 on acidification, while there is a greater resistance to C02 loss when the carbonate is a bridging ligand. Unidentate carbonate complexes decarboxylate with the initial formation of a bicarbonate intermediate and subsequent loss of C02 without rupture of the M—O bond, viz. structure (3). By contrast, in chelate carbonate complexes, cleavage of the M—O bond occurs (with ring opening) with the formation of a bicarbonate aqua ion before the loss of C02, viz. equation (5).29... 

The metal-bound RCN group is also activated on coordination towards nucleophilic attack by alcohols, thiols or amines to give stable N-bonded iminoether, iminothioether and amidine complexes respectively.332 Several cationic cyanobenzylpalladium(II) complexes have been prepared, and the reactivity of the CN group towards nucleophiles has been studied.333,334 The palladium complex (97) reacts with aromatic amines to give chelated amidino complexes (98) and the reaction has been studied kinetically.333 In this case intermediates with the nitrile group bonded side-on are considered to be involved. 

Figure 2.22. Strategies for the transition metal-templated synthesis of catenanes. The metal (in) predisposes two fragments as open chelates (A) (strategy I) or as a macrocyclic chelate (E) and an open chelate (strategy II) in intermediates (B) and (F), respectively. Cyclization of these intermediate complexes with the chain fragments (C) provides the [2]-catenate complex (D).

The reaction of SO2 with rf dioxygen complexes gives a chelated sulphate complex. Isotopic labelling studies with 62 show that one of the terminal oxygen atoms of the sulphate originates from the dioxygen complex and the other from the SO2. This has been interpreted in terms of the rearrangement of a five membered cyclic intermediate . ... 

Alder reactions, in most instances titanium or aluminum Lewis acids afford greater yields and/or selectivity. The stereoselectivity in Lewis acid-promoted Diels-Alder reactions between chiral a,/3-unsaturated A/-acyloxazolidinones results in unexpected selectivity as a function of the nature of the Lewis acid (Table 4) [102]. Optimum selectivity is expected for chelated intermediates, yet both SnCU and TiCU perform poorly relative to Et2AlCl (1.4 equiv.). The formation of the SnCU-A-acyloxazolidi-none chelate has been confirmed by solution NMR studies [103]. These data suggest that other factors such as the steric bulk associated with complexes might contribute to stereoselectivity. 

The diastereoselectivity of reduction of a series of symmetrical diketones to the corresponding diols revealed an intriguing dependance on the separation of the carbonyl groups, but the selectivity was not generally useful. However, in the case of 1,3-diketone (71) lithium borohydride alone produced the anti isomer (70) with 91% diastereoselectivity, but prior addition of titanium tetrachloride gave the syn-diol (72) with 96% diastereoselectivity via a chelated intermediate analogous to the crystalline complex between the diketone and TiCU (Scheme 11). ... 

Less acidic than Ti and Zi chloroderivatives, MeTi(OPr )3 perfoims chelation-controlled addition to chiral alkoxy ketones as well as or better than organomagnesium compounds, but fails to chelate to aldehydes or hindered ketones. Should the formation of a cyclic chelation intermediate be forbidden, the reaction is subject to nonchelation control, according to Ae Felkin-Anh (or Comforth) model. Under these circumstances, the ratio of the diastereomeric products is inverted in favor of the anti-Cram product(s). In the case of benzil (83 Scheme 7) this can be accounted for by the unlikely formation of a cyclic intermediate such as (85), and thus the preferential intermediacy of the open chain intermediate (86) that leads to the threo compound (88). This view is substantiated by the fact that replacement of titanium with zirconium, which is characterized by longer M—O bonds, restores the possibility of having a cyclic intermediate and, as a consequence, leads to the erythro meso) compound (87) thus paralleling the action of Mg and Li complexes. 

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