Ketenes bonding

Acyl(imidoyl)ketenes bearing the acyl and imidoyl groups conjugated with the (2=C ketene bond is an interesting precursor for [4 + 2] cycloaddition reactions. Such compoimds can be subjected to a wide variety of [4 4- 2] cycloaddition reactions, interestingly as either a dienophile with... 

Figure 4.3 Correlation of carbene singlet-triplet energy differences and ketene bond-dissociation energies. Reprinted with permission from the American Chemical Society.

A titanium complex, carbonyl bis( / -cyclopentadienyl)(j -diphenylacetylene)-titanium (5) has been structurally characterized. The Ti—C distances to the acetylene are 2.107(7) and 2.230(7) A, respectively. The long central Ti—C bond is thought to be caused by the proximity of the carbonyl group. Another titanium complex containing a ketene bonded to the metal has had its structure... 

The oxidation of the cyclic enol ether 93 in MeOH affords the methyl ester 95 by hydrolysis of the ketene acetal 94 formed initially by regioselective attack of the methoxy group at the anomeric carbon, rather than the a-alkoxy ketone[35]. Similarly, the double bond of the furan part in khellin (96) is converted ino the ester 98 via the ketene acetal 97[l23],... 

In the presence of a double bond at a suitable position, the CO insertion is followed by alkene insertion. In the intramolecular reaction of 552, different products, 553 and 554, are obtained by the use of diflerent catalytic spe-cies[408,409]. Pd(dba)2 in the absence of Ph,P affords 554. PdCl2(Ph3P)3 affords the spiro p-keto ester 553. The carbonylation of o-methallylbenzyl chloride (555) produced the benzoannulated enol lactone 556 by CO, alkene. and CO insertions. In addition, the cyclobutanone derivative 558 was obtained as a byproduct via the cycloaddition of the ketene intermediate 557[4I0]. Another type of intramolecular enone formation is used for the formation of the heterocyclic compounds 559[4l I]. The carbonylation of the I-iodo-1,4-diene 560 produces the cyclopentenone 561 by CO. alkene. and CO insertions[409,4l2]. 

The alkylphenylacetyi chloride 843 and benzoyl chloride undergo decarbo-nylative cross-condensation to give the enone 845 in the presence of EtiNf723]. The reaction is e.xplained by the insertion of the ketene 844 into the Pd-aryl bond and, 3-elimination. To support this mechanism, o, d-unsaturuted ketones are obtained by the reaction of ketenes with aroyl chlorides[724]. 

Diphenylketene (253) reacts with allyl carbonate or acetate to give the a-allylated ester 255 at 0 °C in DMF, The reaction proceeds via the intermediate 254 formed by the insertion of the C = C bond of the ketene into 7r-allylpalla-dium, followed by reductive elimination. Depending on the reaction conditions, the decarbonylation and elimination of h-hydrogen take place in benzene at 25 °C to afford the conjugated diene 256(155]. 

Allylic phosphates are used for carbonylation in the presence of amines under pressure. Carbonylation of diethyl neryl phosphate (389) affords ethyl homonerate (390), maintaining the geometric integrity of the double bond[244]. The carbonylation of allyl phosphate in the presence of the imine 392 affords the /3-lactam 393. The reaction may be explained by the formation of the ketene 391 from the acyl phosphate, and its stereoselective (2 + 2] cycloaddition to the imine 392 to give the /3-lactam 393(247],... 

Ketenes are oxo compounds with cumulated carbonyl and carbon—carbon double bonds of the general stmcture R R2C—C—O, where and R2 may be any combination of hydrogen, alkyl, aryl, acyl, halogen, and many other functional groups. Ketenes with R = sometimes called aldoketenes,... 

The chemistry of ketenes is dominated by their high reactivity most of them are not stable under normal conditions, many exist only as transient Species. Nucleophilic attack at the j -carbon, [2 + 2] cycloadditions, and ketene iasertion iato single bonds are the most important and widely used reactions of such compounds. 

Ketenes and related compounds have been reviewed extensively (1 9). For the synthesis and synthetic uses of conjugated ketenes see Reference 10. Ketenes with three or more cumulated double bonds have been prepared (11,12). The best known is carbon suboxide [504-64-3] 3 2 preparative uses and has been reviewed (13—16). Thioketenes (17,18), ketenimines (19—21), and their dimers show interesting reactivity, but they have not achieved iadustrial importance to date. 

Chemical Properties. The chemistry of ketenes is dominated by the strongly electrophilic j/)-hybridi2ed carbon atom and alow energy lowest unoccupied molecular orbital (LUMO). Therefore, ketenes are especially prone to nucleophilic attack at Cl and to [2 + 2] cycloadditions. Less frequent reactions are the so-called ketene iasertion, a special case of addition to substances with strongly polarized or polarizable single bonds (37), and the addition of electrophiles at C2. For a review of addition reactions of ketenes see Reference 8. 

Cyclo ddltion. Ketenes are ideal components ia [2 + 2] cycloadditions for additions to the opposite sides of a TT-system as shown ia the cyclobutane product (2) ia Figure 1. Electron-rich double bonds react readily with ketenes, even at room temperature and without catalysts. In conjugated systems, ketenes add ia a [2 + 2] fashion. This is illustrated ia the reaction foUowiag, where the preferential orientation of L (large substituent) and S (small substituent) is seen (40). This reaction has been used ia the synthesis of tropolone [533-75-5]. 

Simple olefins do not usually add well to ketenes except to ketoketenes and halogenated ketenes. Mild Lewis acids as well as bases often increase the rate of the cyclo addition. The cycloaddition of ketenes to acetylenes yields cyclobutenones. The cycloaddition of ketenes to aldehydes and ketones yields oxetanones. The reaction can also be base-cataly2ed if the reactant contains electron-poor carbonyl bonds. Optically active bases lead to chiral lactones (41—43). The dimerization of the ketene itself is the main competing reaction. This process precludes the parent compound ketene from many [2 + 2] cyclo additions. Intramolecular cycloaddition reactions of ketenes are known and have been reviewed (7). 

Ketene Insertions. Ketenes insert into strongly polarized or polarizable single bonds, such as reactive carbon—halogen bonds, giving acid hahdes (7) and into active acid haUdes giving haUdes of p-ketoacids (8) (46). Phosgene [77-44-5] (47) and thiophosgene [463-71-8] (48) also react with ketenes. 

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). 

Union Carbide abandoned the ketene—crotonaldehyde route in 1953 in favor of the oxidation of 2,4-hexadienal made by acetaldehyde condensation. A silver compound used as the catalyst prevented peroxidation of the ethylenic bonds (39,40). Thein plant operated until 1970. 

The reaction of ketene itself with tettaalkyl titanates followed by a ketone R R C=0 gives P-hydroxy-esters, R R C0HCH2C02R. Polyinsertion of ketene and aldehyde into the Ti—O bond leads to di-, tri-, and tetraesters, eg, H0CR R CH2C02CR R CH2C02R (200). 

The structure of the unusual betaine (50) has been determined (70JHC895). The bond lengths and angles suggest that a significant contribution to the structure is made by a resonance form (SOb) in which the N(l)—C(5) bond does not exist ( ketene form). 

Unsubstituted 3-alkyl- or 3-aryl-isoxazoles undergo ring cleavage reactions under more vigorous conditions. In these substrates the deprotonation of the H-5 proton is concurrent with fission of the N—O and C(3)—-C(4) bonds, giving a nitrile and an ethynolate anion. The latter is usually hydrolyzed on work-up to a carboxylic acid, but can be trapped at low temperature. As shown by Scheme 33, such reactions could provide useful syntheses of ketenes and /3-lactones (79LA219). 

The 27T-electrons of the carbon-nitrogen double bond of 1-azirines can participate in thermal symmetry-allowed [4 + 2] cycloadditions with a variety of substrates such as cyclo-pentadienones, isobenzofurans, triazines and tetrazines 71AHC(13)45). Cycloadditions also occur with heterocumulenes such as ketenes, ketenimines, isocyanates and carbon disulfide. It is also possible for the 27r-electrons of 1-azirines to participate in ene reactions 73HCA1351). 

Methylene from diazirine has higher energy of vibration than the product from photolysis of ketene, but it is more discriminating in insertion reactions into primary and secondary C—H bonds. 

The highest priority ring disconnective T-goals for 272 are those which disconnect a cocyclic 5,5-fusion bond and offexendo bond pair. The internal ketene-olefin cycloaddition in tactical combination with the Baeyer-Villiger transform is well suited to the double disconnection of such a cyclopentane-y-lactone ring pair. 

Although these reactions are thus closely related to the acyl-alkyl diradical disproportionation to ketenes, the stereospecificity of (55) -> (56) and (57) -> (58) shows that these hydroxyketones cannot proceed through free radicals capable of rotating about single bonds prior to the intramolecular hydrogen... 

Four-membered heterocycles are easily formed via [2-I-2] cycloaddition reac tions [65] These cycloaddmon reactions normally represent multistep processes with dipolar or biradical intermediates The fact that heterocumulenes, like isocyanates, react with electron-deficient C=X systems is well-known [116] Via this route, (1 lactones are formed on addition of ketene derivatives to hexafluoroacetone [117, 118] The presence of a trifluoromethyl group adjacent to the C=N bond in quinoxalines, 1,4-benzoxazin-2-ones, l,2,4-triazm-5-ones, and l,2,4-tnazin-3,5-diones accelerates [2-I-2] photocycloaddition processes with ketenes and allenes [106] to yield the corresponding azetidine derivatives Starting from olefins, fluonnaied oxetanes are formed thermally and photochemically [119, 120] The reaction of 5//-l,2-azaphospholes with fluonnated ketones leads to [2-i-2j cycloadducts [121] (equation 27)... 

Examine the eleetrostatie potential map for ketene. Which (non-hydrogen) atom is most eleetron poor, and which regions around this atom are most electron poor After oxygen, which atom is most electron rich, and which regions are most electron rich Account for these data with a diagram that shows the orbitals on each atom, their orientation and electron occupancy, and whether or not they participate in covalent bonds (assume that oxygen is sp hybridized). 

Step through the sequence of structures representing dissociation oiketene to methylene and carbon monoxide. Plot energy (vertical axis) vs. carbon-carbon bond distance (horizontal axis). Would you describe ketene as a weak complex between singlet methylene and carbon monoxide Explain. (A table of CC and CO bond lengths is found at left.) Is there an energy barrier to the dissociation ... 

Honk et al. concluded that this FMO model imply increased asynchronicity in the bond-making processes, and if first-order effects (electrostatic interactions) were also considered, a two-step mechanisms, with cationic intermediates become possible in some cases. It was stated that the model proposed here shows that the phenomena generally observed on catalysis can be explained by the concerted mechanism, and allows predictions of the effect of Lewis acid on the rates, regioselectivity, and stereoselectivity of all concerted cycloadditions, including those of ketenes, 1,3-dipoles, and Diels-Alder reactions with inverse electron-demand [2],... 

The ketocarbene 4 that is generated by loss of Na from the a-diazo ketone, and that has an electron-sextet, rearranges to the more stable ketene 2 by a nucleophilic 1,2-shift of substituent R. The ketene thus formed corresponds to the isocyanate product of the related Curtius reaction. The ketene can further react with nucleophilic agents, that add to the C=0-double bond. For example by reaction with water a carboxylic acid 3 is formed, while from reaction with an alcohol R -OH an ester 5 is obtained directly. The reaction with ammonia or an amine R -NHa leads to formation of a carboxylic amide 6 or 7 ... 

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