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Ketene ligands

The molybdenum-acyl enolate 4 has been characterized spectroscopically by NMR and has been reported to exist as a single (observable) isomer88. Extended Hiickel calculations on model complexes suggest that a conformation similar to A is most favorable for enolates such as 488. The deprotonated di-hapto acyl ligand may also be described as a 2-(C,0)-ketene ligand both the ketene and enolate terminology appear in the literature. [Pg.961]

Diphenyl ketene reacts with 39 to yield what has been described as a metal-anchored olefin complex (40) (109). The latter contains a diphenyl ketene ligand which is tj2-C,0 (a metallocyclopropene) -bonded to the (r)-C5H5)2Ti unit. Upon treatment of 40 with protic acids, carbon mon-... [Pg.37]

Carbon monoxide insertion into an osmium-carbon bond of a trinuclear cluster has been reported to give a cluster containing a t-ketene ligand ... [Pg.621]

E3.3 Generation and reactivity of ketene ligands on triosmium clusters... [Pg.1733]

The ketene ligand of (Y-C5H4SiMe3)2Nb(H)(Ti2-OCCHi2) i converted to a vinylidene by oxygen atom transfer to RCN (R = Me or Bu ). The reverse reaction is accomplished by treating... [Pg.240]

Reaction of [0s2(C0) q(w2"8)23 with vinyl acetate gives (131) as the major product together with small quantities of (128) (R=H). The bridging ketene ligand in cluster (132) is converted to an enolate ligand by reaction with... [Pg.336]

The interconversion of methylene and ketene ligands on a triosmium duster was reported. It was found that a triosmium methylene complex in CH2CI2 solution readily adds two moles of carbon monoxide at 22 °C to yield the ketene derivative 9 (reaction 8.29). The formation of the ketene complex 9 from the methylene complex can be made reversible by heating under reduced pressure. Labeling experiments have shown that the ketene carbonyl derives from one of the initial Os3(CO)ii(p-CH2) carbonyl ligands and not from the added CO. This implies a preequilibrium between Os3(CO)xi(p-CH2) and a coordinatively unsaturated ketene complex that subsequently adds two moles of carbon monoxide to give the isolated product 9 [57,58],... [Pg.208]

G.L., Fultz. W.C. and Rheingold. A.L. (1983) Interconversion of methylene and ketene ligands on a triosmium cluster. Crystal and molecular structure of the ketene complex Os3(CO)]2(t -(C.C). j-CH2CO). Journal of the American Chemical Society, 105,... [Pg.219]

A more eflicient and general synthetic procedure is the Masamune reaction of aldehydes with boron enolates of chiral a-silyloxy ketones. A double asymmetric induction generates two new chiral centres with enantioselectivities > 99%. It is again explained by a chair-like six-centre transition state. The repulsive interactions of the bulky cyclohexyl group with the vinylic hydrogen and the boron ligands dictate the approach of the enolate to the aldehyde (S. Masamune, 1981 A). The fi-hydroxy-x-methyl ketones obtained are pure threo products (threo = threose- or threonine-like Fischer formula also termed syn" = planar zig-zag chain with substituents on one side), and the reaction has successfully been applied to macrolide syntheses (S. Masamune, 1981 B). Optically pure threo (= syn") 8-hydroxy-a-methyl carboxylic acids are obtained by desilylation and periodate oxidation (S. Masamune, 1981 A). Chiral 0-((S)-trans-2,5-dimethyl-l-borolanyl) ketene thioketals giving pure erythro (= anti ) diastereomers have also been developed by S. Masamune (1986). [Pg.62]

Silyl enol ethers are other ketone or aldehyde enolate equivalents and react with allyl carbonate to give allyl ketones or aldehydes 13,300. The transme-tallation of the 7r-allylpalladium methoxide, formed from allyl alkyl carbonate, with the silyl enol ether 464 forms the palladium enolate 465, which undergoes reductive elimination to afford the allyl ketone or aldehyde 466. For this reaction, neither fluoride anion nor a Lewis acid is necessary for the activation of silyl enol ethers. The reaction also proceed.s with metallic Pd supported on silica by a special method[301j. The ketene silyl acetal 467 derived from esters or lactones also reacts with allyl carbonates, affording allylated esters or lactones by using dppe as a ligand[302]... [Pg.352]

Allylic acetates react with ketene silyl acetals. In this reaction, in addition to the allylated ester 468, the cyclopropane derivative 469. which is formed by the use of bidentate ligands, is obtained[303]. Formation of a cyclopropane derivative 471 has been observed by the stoichiometric reaction of the 7r-allylpal-... [Pg.352]

Ketenes can react in several ways with organometaUic compounds and complexes. They can add as ligands to coordinated metals forming stable ketene, ketenyl, and ketenyfldene complexes. Ketenes can be inserted into metal—hydride, metal—alkyl, metal—OR, and metal—NR2 bonds, react with metal—oxide complexes, and with coordinated Hgands. This chemistry has been reviewed (9,51). [Pg.475]

The superior donor properties of amino groups over alkoxy substituents causes a higher electron density at the metal centre resulting in an increased M-CO bond strength in aminocarbene complexes. Therefore, the primary decarbo-nylation step requires harsher conditions moreover, the CO insertion generating the ketene intermediate cannot compete successfully with a direct electro-cyclisation of the alkyne insertion product, as shown in Scheme 9 for the formation of indenes. Due to that experience amino(aryl)carbene complexes are prone to undergo cyclopentannulation. If, however, the donor capacity of the aminocarbene ligand is reduced by N-acylation, benzannulation becomes feasible [22]. [Pg.131]

The existence of ketenes was established over a hundred years ago, and, in recent years, asymmetric synthesis based on [2 + 2] cycloadditions of ketenes with carbonyl compounds to form chiral p-lactones has been achieved with high yields and high stereoselectivities. In 1994, Miyano et al. reported the use of Ca-symmetric bis(sulfonamides) as ligands of trialkylaluminum complexes to promote the asymmetric [2 + 2] cycloaddition of ketenes with aldehydes. The corresponding oxetanones were obtained in good yields and enantioselectivities... [Pg.304]

Scheme 2.9 gives some examples of use of enantioselective catalysts. Entries 1 to 4 are cases of the use of the oxazaborolidinone-type of catalyst with silyl enol ethers and silyl ketene acetals. Entries 5 and 6 are examples of the use of BEMOL-titanium catalysts, and Entry 7 illustrates the use of Sn(OTf)2 in conjunction with a chiral amine ligand. The enantioselectivity in each of these cases is determined entirely by the catalyst because there are no stereocenters adjacent to the reaction sites in the reactants. [Pg.131]

Fig. 32. Dendritically enlarged diamines 90-92 and benzylated ligand 93 (DDB analogs) in the enantioselective addition of methanol to ketene using 0.01 equiv. catalyst [114]... Fig. 32. Dendritically enlarged diamines 90-92 and benzylated ligand 93 (DDB analogs) in the enantioselective addition of methanol to ketene using 0.01 equiv. catalyst [114]...
At the present, the most straightforward mechanism for the formation of J5 from 1 is via insertion of CO into the Th-C(acyl) bond to form a ketene (H, (eq. (4)) which subsequently dimerizes. Presumably, initial CO interaction could involve coordination either to the metal ion as shown or to the electrophilic vacant "carbene p atomic orbital. Considering the affinity of the Th(IV) ion for oxygenated ligands, interaction of the ketene oxygen atom with the metal ion seems reason-... [Pg.65]

The Lewis acid catalyst 53 is now referred to as the Narasaka catalyst. This catalyst can be generated in situ from the reaction of dichlorodiisopropoxy-titanium and a diol chiral ligand derived from tartaric acid. This compound can also catalyze [2+2] cycloaddition reactions with high enantioselectivity. For example, as depicted in Scheme 5-20, in the reaction of alkenes bearing al-kylthio groups (ketene dithioacetals, alkenyl sulfides, and alkynyl sulfides) with electron-deficient olefins, the corresponding cyclobutane or methylenecyclobu-tene derivatives can be obtained in high enantiomeric excess.18... [Pg.281]

Chiral dirhodium(II) catalysts with carboxylate or carboxamidate ligands have recently been developed to take advantage of their versatility in metal carbene transformation, and these have now become the catalysts of choice for cyclopropanation. Chiral carboxylate ligands 195,103 196,104 and 197105 have been used for tetrasubstitution around a dirhodium(II) core. However, the enantioselectivity in intermolecular reactions with simple ketenes is marginal. [Pg.316]

In addition to the ring opening of cyclopropenes noted above, vinylketene complexes 103 have been prepared by (1) ligand initiated carbonyl insertion of vinyl carbene complexes 104 and (2) benzoylation of ,/3-unsaturalcd acyl ferrates 105 (Scheme 20)114. X-ray diffraction analysis of these vinylketene complexes indicates that the structure may be best represented as a hybrid between an /j4-dicnc type complex (103) and an jj3-allyl r/1 acyl complex (106). The Fe-Cl distance (ca 1.92 A) is shorter than the Fe-C2, Fe-C3, or Fe-C4 distances (ca 2.1-2.2 A)113a-C. In addition, the C—C—O ketene array is not linear (bend angle ca 135°). [Pg.921]

Vollhardt s investigations100 into electrocyclic transformations on a CpCo template produced the following unusual result. After photolysis of CpCo(CO)2 in the presence of the tosyl hydrazone of trans-4-pheny -3-buten-2-one, the only isolated product was the vinylketene complex 123. Note that the tricarbonyliron analogue of this complex has also been isolated.3,87 The mechanism of formation was not discussed, but it seems likely that the ketene carbonyl originated as a carbonyl ligand that replaced the hydrazone moiety, perhaps via a vinylcarbene intermediate. [Pg.307]

Weiss studied68a the reactivity of both new complexes, and found that a variety of phosphines and phosphites would also convert the vinylcarbene complex 139 into the corresponding vinylketene complex (140), capturing one of the carbonyl ligands from the coordination sphere of the metal to become the ketene carbonyl. Only in the case of triphenylphosphine was the dicarbonyl(phosphine)vinylcarbene complex (141) isolated, which then required addition of carbon monoxide to convert it to the dicarbonyl(triphe-nylphosphine)vinylketene complex 140.a. This interconversion was reversible and proceeded quantitatively. [Pg.312]


See other pages where Ketene ligands is mentioned: [Pg.502]    [Pg.168]    [Pg.9]    [Pg.2963]    [Pg.2965]    [Pg.493]    [Pg.289]    [Pg.2962]    [Pg.2964]    [Pg.1031]    [Pg.335]    [Pg.507]    [Pg.221]    [Pg.312]    [Pg.502]    [Pg.168]    [Pg.9]    [Pg.2963]    [Pg.2965]    [Pg.493]    [Pg.289]    [Pg.2962]    [Pg.2964]    [Pg.1031]    [Pg.335]    [Pg.507]    [Pg.221]    [Pg.312]    [Pg.353]    [Pg.41]    [Pg.102]    [Pg.250]    [Pg.298]    [Pg.118]    [Pg.171]    [Pg.371]    [Pg.265]    [Pg.287]    [Pg.288]    [Pg.293]    [Pg.303]   
See also in sourсe #XX -- [ Pg.1031 ]




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