Palladium-catalyzed Heck-type Carbonylation Of Olefins With Amine Chloride

Transition metal-catalyzed carbonylation reactions has become an ideal tool for the preparation of carbonyl-containing compounds due to their relatively mild reaction conditions and efficient atomic utilization.Carbon monoxide（CO）is one of the most important C1 source in synthetic chemistry.Considering the factors of operability and safety,the usage of various CO surrogates for carbonylative reactions has been developed in recent years.Thus,it’s essential to develop efficient carbonylative transformations for the construction of complex carbonyl-containing chemicals from readily available starting materials and CO surrogates.In this thesis,we developed palladium-catalyzed Heck carbonylation reaction of alkene-tethered carbamoyl chlorides to synthesis a variety of functionalized oxindoles/lactams by utilizing Mo（CO）₆ as convenient CO surrogates.1.Synthesis of amide-functionalized oxindoles/lactamsWe realized the palladium-catalyzed carbonyl-amidation of alkene-tethered carbamoyl chlorides,which utilizes Mo（CO）₆ as convenient CO surrogates.Diversiform amidated oxindoles/γ-lactams bearing an all-carbon quaternary stereocenter were synthesized in moderate to good yields with good functional group tolerance.2.Synthesis of ester/carboxyl-functionalized oxindoles/lactamsWe reported palladium-catalyzed Heck carbonylation reaction of alkene-tethered carbamoyl chlorides using Mo（CO）₆ as the carbonyl source.The reactions were typically performed with good functional group compatibility and tolerated different nucleophiles（alcohols,thiols and water）,which provided a new access to esterificated/thioesterificated/carboxylated oxindoles or lactams under gas-free conditions.Furthermore,natural product mutations and divergent late-stage derivatization are the important practical features.