Palladium(0)-Catalyzed Reactions of Nucleophiles with Allyl Carbonates of Unsaturated Fatty Acids

Schäfer, Hans J.; Zobel, M.

doi:10.1201/9781439832073.ch4

Cited by 5 publications

(3 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This way with the O-nucleophiles: methanol, phenols, carbohydrates, a-tocopherol, and estradiol the corresponding substitution products were obtained as mixture of regioisomers ( Table 2, Nr. [1][2][3][4][5][6][7][8][9][10][11][12]. With the N-nucleophiles: picolylamine and piperidine, and the C-nucleophiles: dimethyl malonate, nitromethane, methyl acetoacetate, and malodinitrile the corresponding Pd(0)catalyzed C-N-and C-C-bond formations could be achieved ( Table 2, Nr.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of fatty acid conjugates with phenols, carbohydrates, amines, and CH‐acidic compounds by Pd(0)‐catalyzed allylic substitution

Zobel

Schäfer

2016

Euro J Lipid Sci & Tech

Self Cite

View full text Add to dashboard Cite

The efficiency of a pharmaceutical can be increased by connecting it to a fatty acid. Nucleophilic allylic substitution of methyl 10‐undecenoate and methyl oleate with palladium(0) as catalyst is explored to see, whether this reaction is useful for such connections with regard to yield and selectivity. For that purpose the allylic CH‐bonds in methyl 10‐undecenoate and methyl oleate were oxidized with selenium dioxide and tert‐butylhydroperoxide. The obtained allylic alcohols were then activated by conversion into their methyl carbonates. Allylic substitution was performed with O‐nucleophiles as methanol, carbohydrates, and different phenols as α‐tocopherol and estradiol; furthermore N‐ and C‐nucleophiles were applied. The yields of substitution products were in the range of 37–98%. High yields of conjugates were obtained with phenols, even when the hydroxy group was sterically shielded. These conjugates have an ether bond, a CN or a CC bond as link. They should have the advantage to be more stable in body fluids than the frequently applied conjugates being connected by the less inert ester bond. Triesters and dicyanoesters obtained with C‐nucleophiles can be possibly used as cross linkers for polyesters and polyamides. Practical applications: These conjugates should be more stable in cells and body fluids than the frequently applied conjugates being connected by the less inert ester bond. Triesters and dicyanoesters obtained with C‐nucleophiles can be possibly used as cross linkers for polyesters and polyamides. Methyl 9‐hydroxy‐10‐undecenoate is prepared by allylic oxidation from methyl 10‐undecenoate. After esterification to the methyl carbonate this leaving group is substituted via Pd(0)‐catalysis by O‐, N‐, and C‐nucleophiles to afford fatty acid conjugates. Similarly methyl oleate is converted.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Our earlier work is reported in Refs. . Further syntheses of conjugates with fatty acids and with a carbohydrate using other strategies are described in Refs.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of fatty acid conjugates with phenols, carbohydrates, amines, and CH‐acidic compounds by Pd(0)‐catalyzed allylic substitution

Zobel

Schäfer

2016

Euro J Lipid Sci & Tech

Self Cite

View full text Add to dashboard Cite

show abstract

“…Other strategies for the selective synthesis of branched fatty acid derivatives include alkene radical additions as reported by Metzger [12][13][14][15][16][17] and others [18], palladium(0)catalyzed nucleophilic additions of dimethyl malonate, nitromethane and methyl acetylacetate [19], zeolite-mediated isomerizations of oleic or tallow fatty acids leading to methyl-and ethyl-branched unsaturated fatty acids [20], and electrophilic additions of alkyl chloroformates in the presence of Lewis acids such as ethylaluminum sesquichloride [21,22].…”

Section: Introductionmentioning

confidence: 99%

Selective synthesis of propenyl‐branched diunsaturated fatty esters via catalytic codimerization of ethyl linoleate and propylene

Erb¹,

Dierker

Ohlmann

et al. 2015

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

A bimetallic catalyst system consisting of RhCl3 and Pd(MeCN)2Cl2 efficiently promotes the conversion of ethyl linoleate selectively to mono‐propenylated diunsaturated products. The reaction proceeds in high yields under mild conditions. The key advantage of the new process is that it is based on the readily available linoleate rather than a preformed conjuenic acid ester. Practical applications: The new protocol opens up a high yielding and environmentally friendly method for the introduction of side chains with a defined length into fatty acid derivatives. The products are of profound potential interest for industrial applications, e.g., in lubricants, cosmetics, plastics, and coatings, as branched fatty acids are known to have a lower solidifying point and viscosity and an increased solubility than their linear counterparts. Rh/Pd‐catalyzed selective conversion of ethyl linoleate to mono‐propenylated diunsaturated products under mild conditions.

show abstract

Neue Synthesen mit Ölen und Fetten als nachwachsende Rohstoffe für die chemische Industrie

Biermann¹,

Friedt²,

Lang³

et al. 2000

Angewandte Chemie

View full text Add to dashboard Cite

Palladium(0)-Catalyzed Reactions of Nucleophiles with Allyl Carbonates of Unsaturated Fatty Acids

Cited by 5 publications

References 25 publications

Synthesis of fatty acid conjugates with phenols, carbohydrates, amines, and CH‐acidic compounds by Pd(0)‐catalyzed allylic substitution

Synthesis of fatty acid conjugates with phenols, carbohydrates, amines, and CH‐acidic compounds by Pd(0)‐catalyzed allylic substitution

Selective synthesis of propenyl‐branched diunsaturated fatty esters via catalytic codimerization of ethyl linoleate and propylene

Neue Synthesen mit Ölen und Fetten als nachwachsende Rohstoffe für die chemische Industrie

Contact Info

Product

Resources

About