Stereocontrolled Lactonization Reactions via Palladium-Catalyzed 1,4-Addittion to Conjugated Dienes

Stereocontrolledp alladium(I1)-catalyzed1 ,4-chloro-and 1,4-acetoxylactonizations o f conjugated cyclic dienes have been developed to give stereodefined fused lactones. The stereochemistry of the 1,4- acetoxylactonization was controlled by the ligand on the metal catalyst, and in this way either a cisor truns-acetoxylactonization was obtained. This dual stereoselectivity is explained by a stereocontrolled acetate attack (trans or cis, respectively) on the allyl group in the catalytic (π-allyl)- palladium intermediate. To further strengthen the mechanism the intermediate (π-ally1)palladium complex was isolated and fully characterized. A stereospecific synthesis of cis- and truns-2-[6- (benzyloxy)-2,4-heptadien-l-yllacetic a cid (cis- and truns-9) followed by stereoselective Pd(I1)- catalyzed chloro- and acetoxylactonization in acetonelacetic acid resulted in highly functionalized fused lactones with control of the relative stereochemistry at four different carbons.

Granberg, Kennth L. (författare)
Andersson, PherUppsala universitet,Organisk kemi I(Swepub:uu)phergas (författare)
Gatti, Roberto (författare)
Gogoll, AdolfUppsala universitet,Organisk kemi I(Swepub:uu)adolfgog (författare)
Uppsala universitetOrganisk kemi I (creator_code:org_t)

Ingår i:Journal of Organic Chemistry: American Chemical Society (ACS)58:20, s. 5445-54510022-32631520-6904

Av författaren/redakt...: Bäckvall, Jan-E.; Granberg, Kennth ...; Andersson, Pher; Gatti, Roberto; Gogoll, Adolf

Om ämnet

Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.