73062-33-6Relevant articles and documents
Oxime palladacycle-catalyzed Suzuki-Miyaura alkenylation of aryl, heteroaryl, benzyl, and allyl chlorides under microwave irradiation conditions
Civicos, Jose F.,Alonso, Diego A.,Najera, Carmen
supporting information; experimental part, p. 1683 - 1687 (2011/09/19)
A simple new protocol for the palladium-catalyzed Suzuki-Miyaura cross-coupling of organic chlorides under microwave irradiation is presented. Deactivated aryl and heteroaryl chlorides are efficiently cross-coupled with alkenylboronic acids and potassium alkenyltrifluoroborates using the 4,4′-dichlorobenzophenone oxime-derived palladacycle 1b as precatalyst in 0.1 to 0.5 mol% palladium loading, tris(tert-butyl)phosphonium tetrafluoroborate {[HP(t-Bu)3]BF4} as ligand, tetra-n-butylammonium hydroxide as cocatalyst, and potassium carbonate as base in N,N- dimethylformamide at 130°C under microwave irradiation conditions. Under these conditions, styrenes, stilbenes, and alkenylarenes are obtained in good to high yields, and with high regio- and diastereoselectivities in only 20 min. The reported protocol is also very efficient for the regioselective alkenylation of benzyl and allyl chlorides to afford allylarenes and 1,4-dienes. Copyright
Alkylation of Allylic Derivatives. 17. Cross-Coupling Reactions of Diallylic Pivalates with Butyl- and Phenylcopper Reagents
Underiner, Ted L.,Goering, Harlan L.
, p. 2563 - 2572 (2007/10/02)
Cross coupling (Z)-1-phenyl-1,4-pentadien-3-yl pivalate (cis-1-OPiv) with LiCuBu2, LiCu(CN)Bu, LiCuPh2 and LiCu(CN)Ph gives only the fully conjugated γ-coupling product.With LiCuBr2 substantial loss of double-bond configuration occures to give primarily the all-trans coupling product.With other cuprates, no detectable loss of double-bond configuration was observed.Cross coupling (Z)-3-(2-phenylethenyl)-2-cyclohexen-yl pivalate (cis-18-OPiv) with LiCuBu2, LiCuPh2, and LiCu(CN)Ph gives only α coupling product; with LiCu(CN)Bu, a mixture of α, γ, and ε coupling product was obtained.Cross coupling with LiCuBu2 results in loss of double-bond configuration in the α-alkylation product.With other cuprates, no loss of double-bond configuratiuon was detected in the α and γ coupling product.These results have profound mechanistic implications, which are discussed.The relationship between structure and reactivity was also investigated.A variety of diallylic pivalates (1-5-OPiv) were prepared and cross coupled with LiCuBu2, LiCu(CN)Bu, LiCuPh2, and LiCu(CN)Ph.Generally, coupling occurs at the least-substituted allylic system; mechanistic implications are discussed.
