Reference

Palladium-complex-catalyzed reactions of ketenes with allylic carbonates or acetates

Palladium-complex-catalyzed reactions of ketenes with allylic carbonates or acetates. Novel syntheses of a-allylated carboxylic esters and 1,3-dienes. Mitsudo, Takeaki; Kadokura, Mamoru; Watanabe, Yoshihisa (Fac. Eng., Kyoto Univ., Kyoto 606, Japan). J.Some commonly used reagents like 2497-18-9 is used in this experiment. Org. Chem., 52(9), 1695-9 (English) 1987. CODEN: JOCEAH. ISSN: 0022-3263. DOCUMENT TYPE: Journal CA Section: 25 (Benzene, Its Derivatives, and Condensed Benzenoid Compounds) Ph2C:CO and PhCEt:CO react with allylic carbonates or acetates in the presence of a catalytic amt. of (Ph3P)4Pd to give a-allylated esters or 1,3-dienes, resp. E.g., reaction of Ph2C:CO with H2C:CHCH2OCO2Me (I) in DMF at 0° gave Ph2C(CO2Me)CH2CH:CH2 in 67% yield. Reaction of Ph2C:CO with H2C:CHCH2OAc in benzene at 25° gave Ph2C:CHCH:CH2 in 72% yield. Marked solvent effects were obsd. More polar solvents favored the formation of esters from reaction of ketene with allylic carbonates. Formation of the corresponding diene was prevalent in nonpolar solvents. .

Carbonylation of alkyltitanium compounds with allylic derivatives

Carbonylation of alkyltitanium compounds with allylic derivatives. Tsuji, Yasushi; Ishii, Tetsuya (Fac. Eng.In this study， 10596-48-2 and 2497-18-9 are also used., Gifu Univ., Yanagido 501-11, Japan). J. Organomet. Chem., 425(1-2), 41-8 (English) 1992. CODEN: JORCAI. ISSN: 0022-328X. DOCUMENT TYPE: Journal CA Section: 25 (Benzene, Its Derivatives, and Condensed Benzenoid Compounds) Section cross-reference(s): 29 Triisopropoxymethyltitanium or diisopropoxydimethyltitanium (1b) was treated with CO (1 atm, balloon) at room temp. overnight (16-18 h), and then the reaction mixt. was added to various allyl derivs. in the presence of palladium catalyst (5 mol% based on the allylic derivs.) at room temp. From 1b and cinnamyl acetate in the presence of tetrakis(triphenylphosphine)palladium, (E)-3,3-dimethyl-6-phenyl-5-hexen-2-one was afforded in 57% yield. A similar reaction with trans-2-hexenyl acetate also gave the corresponding g,d-unsatd. ketone in 57% yield. The formation of the products would be rationalized by titanium h2-acyl and oxicarbenoid intermediates. .