New rules of selectivity: allylic alkylations catalyzed by palladium

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

“…[242][243][244] The Pd-catalyzed [3+2] cycloaddition reactions of TMM precursors to electron-deficient alkenes have been suggested to proceed via zwitterionic (η 3 -TMM)PdL 2 complexes. [245][246][247][248][249][250] Ten years later, the groups of Wojcicki 251,252 and Chen 253 were the first to isolate and structurally characterize such species. Both, the analogous Pt(η 3 -TMM) (130, eq 36) 251 and Pd(η 3 -TMM) (131, eq 37) 253 254 presumably via metallacyclobutanes, from the reaction of the Fischer carbene complexes (CO) 5 MdC-(OEt)Ph with phenyl allene.…”

Transannular Diels–Alder cyclization of substituted 13-membered trienes. An approach to the B.C.D.[6.6.5] rings of the 14β-hydroxysteroids

“…The alcohol 25 was then transformed into the corresponding acetate 27 (96% yield) and pivaloate 28 (80% yield). The macrocyclization step was carried out on both esters 27 and 28 via their n ally1 palladium complexes (17) to yield the desired macrocycle 29 in 23 and 79% yields, respectively.…”

Dual Amine‐ and Brønsted Acid‐Catalyzed α‐Allylic Alkylation of Aldehydes

“…[1] During the last 30 years, palladium-catalyzed allylic alkylation has become an attractive and mature synthetic method. [2,3] These processes inevitably produce a stoichiometric amount of alcohols or organic waste. The substitution of the halides and related compounds also produces salts waste and requires a stoichometric amount of a base.…”