Alkoxalyl complexes of palladium(II) and platinum(II)

Dobrzynski, Edward D.; Angelici, Robert J.

doi:10.1021/ic50143a012

Cited by 34 publications

(8 citation statements)

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“…[4] We were therefore encouraged by the unique and unexpected stability of RhÀCOCOOR species to explore catalytic addition reactions of ClÀCOCOOR with unsaturated organic compounds. We now report the efficient CO-retentive addition of ClÀCOCOOEt 2 to alkynes 1 affording g-chloro-a-oxob,g-unsaturated esters, [5] catalyzed by rhodium complexes [Eq.…”

Section: Introductionmentioning

confidence: 99%

“…MS analysis revealed that two isomeric octyne trimers were formed in entries 14, 15, and 17. [9] Other complexes such as [Pd-(PPh 3 ) 4 Scope and limitations of the catalytic reactions: The addition reaction can be applied to a variety of alkynes (Table 3). Most aliphatic alkynes, including 3,3-dimethyl-1-butyne, having a sterically demanding substituent react readily to afford the respective adducts in high yields with high regioselectivities (Table 3, entries 1-4).…”

Section: Introductionmentioning

confidence: 99%

“…[4] The resulting complexes, particularly palladium ones, readily undergo decarbonylation resulting in the corresponding alkoxycarbonyl complexes. For instance, decarbonylation of trans-[PdCl(COCOOMe)(PPh 3 ) 2 ] dissolved in CHCl 3 at room temperature is approximately half complete in 10 min and nearly complete in 20 min.…”

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confidence: 99%

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Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes

Hua

Onozawa

Tanaka

2005

Chemistry A European J

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Addition of ethoxalyl chloride (ClCOCOOEt) to terminal alkynes at 60 degrees C in the presence of a rhodium(I)-phosphine complex catalyst chosen from a wide range affords 4-chloro-2-oxo-3-alkenoates regio- and stereoselectively. Functional groups such as chloro, cyano, alkoxy, siloxy, and hydroxy are tolerated. The oxidative addition of ethoxalyl chloride to [RhCl(CO)(PR(3))(2)] proceeds readily at 60 degrees C or room temperature and gives [RhCl(2)(COCOOEt)(CO)(PR(3))(2)] (PR(3) = PPh(2)Me, PPhMe(2), PMe(3)) complexes in high yields. The structure of [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] was confirmed by X-ray crystallography. Thermolysis of these ethoxalyl complexes has revealed that those ligated by more electron-donating phosphines are fairly stable against decarbonylation and reductive elimination. [RhCl(2)(COCOOEt)(CO)(PPh(2)Me)(2)] reacts with 1-octyne at 60 degrees C to form ethyl 4-chloro-2-oxo-3-decenoate. The catalysis is therefore proposed to proceed by oxidative addition of ethoxalyl chloride, insertion of an alkyne into the Cl--Rh bond of the resulting intermediate, and reductive elimination of alkenyl-COCOOEt.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes

Hua

Onozawa

Tanaka

2005

Chemistry A European J

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“…The formation of carbalkoxy species is favoured by a base, e.g. a tertiary amine or a carboxylate anion [5,13,14,16]. It has been suggested that the role of the base is to neutralize the acid that forms in equilibrium (2) and to increase the concentration of MeO-which attacks the coordinated CO to form the PdCOOR moiety [ 171:…”

Section: Resultsmentioning

confidence: 99%

“…It has also been reported that carbalkoxy complexes of the type trans-[Pd(PPh,),(COOR)Cll can be synthesized by carbonylating truns-[Pd(PPh,), Cl,] suspended in an alkanol in the presence of a base such as NEt, [14,16] or PrCOO- [20]. We have found that these complexes (R = Me or Et) can also be synthesized when trans-[Pd (PPh,) is allowed to react with CO under the same conditions, but in the presence of NEt, in place of the ylide [15,17].…”

Section: Resultsmentioning

confidence: 99%

New aspects of the carbonylation of allylpalladium complexes

Bertani¹,

Cavinato²,

Facchin³

et al. 1994

Journal of Organometallic Chemistry

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The carbonylation of (~3-allyl)palladium(II) chloride dimer in the presence of an excess of ylide, such as Ph,PC(H)COR (R = Me or Ph) (Pd: ylide = 1: 5) in MeOH or EtOH, at a CO pressure of 4 atm at room temperature occurs with reduction of the palladium(U) complex to palladium metal and with formation of the corresponding alkyl 3-butenoate with a high yield. The ylide does not give rise to any carbonylation product. When the carbonylation is carried out in the presence of PPh, (Pd: PPh, = 1: 2-3), there is also formation of the unsaturated ester, although in lesser amount, together with [Pd,(PPh,),(CO),](n E 3 or 4) or [Pd(PPh,),(CO)] and trans-[Pd(PPh,),(COOR)CI] (R = Me or Et). These products also form when the carbonylation is carried out in the presence of NJZt, or PrCOONa, in place of the ylide, and of PPh,.It has also been found that [Pd(PPh3),C12] reacts in MeOH or EtOH at a CO pressure of 4 atm at ambient temperature in the presence of an excess of ylide to give the corresponding carbalkoxy complex trans-[Pd(PPh3)JCOOR)C1]. These findings suggest that the ylide probably promotes formation of carbalkoxy species, as do NEt, or PrCOONa because the ylide can behave as a base (pK, = 7). They are strong support for the suggestion that the carbonylation of (allyl)palladium complexes occurs via a (carbalkoxy)palladium species.

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ChemInform Abstract: ALKOXYLYL COMPLEXES OF PALLADIUM(II) AND PLATINUM(II)

Dobrzynski¹,

Angelici²

1975

Chemischer Informationsdienst

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Alkoxalyl complexes of palladium(II) and platinum(II)

Cited by 34 publications

References 30 publications

Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes

Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes

New aspects of the carbonylation of allylpalladium complexes

ChemInform Abstract: ALKOXYLYL COMPLEXES OF PALLADIUM(II) AND PLATINUM(II)

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Alkoxalyl complexes of palladium(II) and platinum(II)

Cited by 34 publications

References 30 publications

Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC2H5 to Alkynes

Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC2H5 to Alkynes

New aspects of the carbonylation of allylpalladium complexes

ChemInform Abstract: ALKOXYLYL COMPLEXES OF PALLADIUM(II) AND PLATINUM(II)

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Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes

Rhodium‐Catalyzed Nondecarbonylative Addition Reaction of ClCOCOOC₂H₅ to Alkynes