Catalyst generations

An important aspect of this procedure is the use of latent acid catalysts, such as phenyl hydrogen maleate, phenyl trifluoracetate, and butadiene sulfone. These catalysts reduce the peak exotherm from over 200°C to 130—160°C. The resin catalyst mixture has a working life of up to several days at RT. The elevated temperature of mol ding these latent catalysts generates the corresponding acids, namely, maleic, trifluoracetic, and phenolsulfonic, which cataly2e the resole reaction. Typically, a cycle time of 1—2 min is requited for a mold temperature of - 150° C. 

With hydrogen sulfide at 500—600°C, monochlorotoluenes form the corresponding thiophenol derivatives (30). In the presence of palladium catalysts and carbon monoxide, monochlorotoluenes undergo carbonylation at 150—300°C and 0.1—20 MPa (1—200 atm) to give carboxyHc acids (31). Oxidative coupling of -chlorotoluene to form 4,4 -dimethylbiphenyl can be achieved in the presence of an organonickel catalyst, generated in situ, and zinc in dipolar aprotic solvents such as dimethyl acetamide (32,33). An example is shown in equation 4. 

Keck et al. reported that a catalyst generated from (S)- or (l )-BINOL 12 and Ti(0-i-Pr)4 in a 2 1 ratio is more selective than the catalyst formed from a 1 1 mixture [19fj. The former catalyst was shown to catalyze the cycloaddition reaction of aldehydes 1 with Danishefsky s diene 2a affording the dihydropyrones 3 with moderate to excellent enantioselectivity (Scheme 4.12). The reaction proceeds well for different aldehydes with up to 97% ee and good yield of the cycloaddition products. 

A syn-selective asymmetiic nih o-aldol reaction has been reported for structurally simple aldehydes using a new catalyst generated from 6,6-bis[(tiiethylsilyl)ethynyl]BINOL (g in Scheme 3.18). The syn selectivity in the nitro-aldol reaction can be explained by steric hindrance in the bicyclic transition state as can be seen in Newman projection. In the favored h ansition state, the catalyst acts as a Lewis acid and as a Lewis base at different sites. In conbast, the nonchelation-controlled transition state affords anti product with lower ee. This stereoselective nitro-aldol reaction has been applied to simple synthesis of t/ireo-dihydrosphingosine by the reduction of the nitro-aldol product with H2 and Pd-C (Eq. 3.79). 

Both the Bronsted and Lewis acid sites on the catalyst generate carbenium ions. The Bronsted site donates a proton to an olefin molecule and the Lewis site removes electrons from a paraffin molecule. In commercial units, olefins come in with the feed or are produced through thermal cracking reactions. 

In an extension of this work, the Shibasaki group developed the novel transformation 48—>51 shown in Scheme 10.25c To rationalize this interesting structural change, it was proposed that oxidative addition of the vinyl triflate moiety in 48 to an asymmetric palladium ) catalyst generated under the indicated conditions affords the 16-electron Pd+ complex 49. Since the weakly bound triflate ligand can easily dissociate from the metal center, a silver salt is not needed. Insertion of the coordinated alkene into the vinyl C-Pd bond then affords a transitory 7t-allylpalladium complex 50 which is captured in a regio- and stereocontrolled fashion by acetate ion to give the optically active bicyclic diene 51 in 80% ee (89% yield). This catalytic asymmetric synthesis by a Heck cyclization/ anion capture process is the first of its kind. 

In the direct coupling reaction (Scheme 30), it is presumed that a coordinatively unsaturated 14-electron palladium(o) complex such as bis(triphenylphosphine)palladium(o) serves as the catalytically active species. An oxidative addition of the organic electrophile, RX, to the palladium catalyst generates a 16-electron palladium(n) complex A, which then participates in a transmetalation with the organotin reagent (see A—>B). After facile trans- cis isomerization (see B— C), a reductive elimination releases the primary organic product D and regenerates the catalytically active palladium ) complex. 

Reactions between imines and a-diazo carboxylates afford aziridine-2-carboxylates [55]. An asymmetric version of this reaction using chiral nonracemic catalysts has been described [53, 56-58]. As an example, catalytic aziridination of inline 44 (Scheme 3.14) with ethyl diazoacetate in the presence of 10% catalyst generated... 

Unfortunately, it is difficult to ascertain the identity of the actual catalytic species, and it is not clear whether catalysis by a true intercalation compound has been established. For instance, a frequent method for ammonia and Fischer-Tropsch catalyst generation is the following ... 

Logical, mixing constraints, to avoid explosive mbctures, poisoning of catalysts, generation of toxic materials, deterioration of product quality, and other consequences resulting from the unintentional mixing of various chemicals. 

Transfer of the hydride from the Cu to the electrophilic carbon and cleavage of the copper alkoxide by the silane regenerates 69. Recent reports point to the influence of the type of the counter ion X" of the homoleptic 66-67 on the activity, the BF being superior to the PF analogue this effect has been attributed to differences in the rate of active catalyst generation from the homoleptic [Cu(NHC)2] X and NaO Bu due to solubility differences of the inorganic salts formed during the displacement of the NHC by BuO" [54] (Scheme 2.10). 

Further insight into the P-borylation reaction of a,P-enones (Scheme 2.32) showed that the reaction can be carried out in THF, and the catalyst generated in situ from CuCl (5 mol%), the imidazolium salt (5 mol%), and NaO Bu (10 mol%), to form the [Cu(O Bu) (NHC)] as the catalysis initiating species. In this case, stable boron enolate products are formed which need to be hydrolysed by methanol to the ketone products [114]. 

Scheme 12.26) [58], Tomiokahas reported a similar procedure using C2-symmetric imidazolinium pre-catalysts, generating products with up to 80% ee [61],... 

The oxazaborolidines B and C derived from proline are also effective catalysts. The protonated forms of these catalysts, generated using triflic acid or triflimide, are very active catalysts,95 and the triflimide version is more stable above 0° C. Another protonated catalyst D is derived from 2-cyclopentenylacetic acid. 

A chiral zirconium catalyst generated from Zr(0,-Bu)4 and (R)-3,3 -diiodo-1,1 -binaphthalene-2,2 -diol [(f )-3,3/-l2BINOL] catalyzed... 

Mussel, tomato Digestion of sample with acid or acid plus catalyst generation of lead hydride GFAAS 4 ng/g g4-g5 Aroza et al. 1080... 

Suslick KS, Fang M, Fly eon T, Cichowlas AA, Gonsalves KE, Chow GM, Xiao TO, Cammarata RC (1994) Nanostructured Fe-Co catalysts generated by ultrasound. Molecular Design Nanostruct Mater 351 443 148... 

The catalytic effect of graphite A thus depends on iron impurities, e. g. Fe304, and probably also on iron sulfides or sulfates, because sulfur is also present in this graphite, and all these iron compounds are known catalysts of FC acylation [69, 73, 74], In this respect, it seems that FeCl3 could be the true catalyst generated in situ by the reaction of the different iron compounds with acid chloride and hydrogen chloride. In the... 

Pd(dba)2 [palladium(O)] generally affords the best results and thus an oxidation to the metal center must occur. The most likely mechanism for this to occur is by net oxidative addition of the acidic phosphonium P-H moiety (Scheme 3). This hypothesis is supported by the observation that the pKa of the phosphonium-hydro-gen bond directly affects the activity of catalysts generated in situ with more basic ligands being inactive. 

Beyond palladium, it has recently been shown that isoelectronic metal complexes based on nickel and platinum are active catalysts for diyne reductive cyclization. While the stoichiometric reaction of nickel(O) complexes with non-conjugated diynes represents a robust area of research,8 only one example of nickel-catalyzed diyne reductive cyclization, which involves the hydrosilylative cyclization of 1,7-diynes to afford 1,2-dialkylidenecyclohexanes appears in the literature.7 The reductive cyclization of unsubstituted 1,7-diyne 53a illustrates the ability of this catalyst system to deliver cyclic Z-vinylsilanes in good yield with excellent control of alkene geometry. Cationic platinum catalysts, generated in situ from (phen)Pt(Me)2 and B(C6F5)3, are also excellent catalysts for highly Z-selective reductive cyclization of 1,6-diynes, as demonstrated by the cyclization of 1,6-diyne 54a.72 The related platinum bis(imine) complex [PhN=C(Me)C(Me)N=Ph]2Pt(Me)2 also catalyzes diyne hydrosilylation-cyclization (Scheme 35).72a... 

The optimized process operates at 80 bar hydrogen and 50 °C with a catalyst generated in situ from [Ir(cod)Cl]2 and the Josiphos ligand PPF-PXyl2 (short name Xyliphos) at a SCR of >1000000. Complete conversion is reached within 3—4h, the initial TOFs exceed 1 800 000 h 1, and the ee is about 80%. This process is now operated by Syngenta on a scale of >10000 ty-1 [127]. 

Treating 2,3-dihydrofuran 68 with aryl triflate 69 in the presence of a base and a palladium catalyst generated in situ from Pd(OAc)2 and (R)-BINAP... 

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