Palladium‐Catalyzed Carbamoyl‐Carbamoylation/ Carboxylation/Thioesterification of Alkene‐Tethered Carbamoyl Chlorides Using Mo(CO)₆ as the Carbonyl Source

Abstract

We reported a palladium‐catalyzed carbamoyl‐carbamoylation/carboxylation/thioesterification 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 (amines, alcohols, phenols, thiols and water), which provided a new access to amidated/esterificated/thioesterificated/carboxylated oxindoles or lactams bearing an all‐carbon quaternary stereocenter under CO gas‐free conditions. Furthermore, natural product mutation and divergent late‐stage derivatization are the important practical features.

Palladium-catalyzed Heck/aminocarbonylation of alkene-tethered carbamoyl chlorides with nitro compounds for the synthesis of carbamoyl-substituted oxindoles

“…Based on the above results and previous reports, 8 a possible reaction mechanism is proposed as shown in Scheme 4. Initially, oxidative addition of Pd 0 L n with alkene-tethered carbamoyl chlorides 1 affords intermediate I , which then undergoes an intramolecular carbopalladation to give alkylpalladium complex II .…”

“…7 Additionally, palladium-catalyzed cyclization and carbonylation reactions of alkene-tethered carbamoyl chlorides with various nucleophiles, such as alcohols, amines, and thiols, provide a necessary supplement for the synthesis of carbonyl-containing compounds bearing oxindole skeletons; however, very limited examples were reported. 8 On the other hand, nitro compounds have recently served as attractive nitrogen sources due to their abundant, stable, and inexpensive properties. 9 Not surprisingly, a variety of transition-metal-catalyzed aminocarbonylation reactions have been developed using nitrogen compounds as nitrogen surrogates.…”

Recent Advances in the Synthesis of Five‐membered Nitrogen Heterocycles Induced by Palladium Ions and Complexes

“…In their recent contribution, compounds 24 b have been applied in carbamoyl‐carbamoylation using Mo(CO) 6 as the carbonyl source [115] . A wide range of products were synthesized bearing amidated functions with the use of SPhos ligand and DBU (18 examples, 50–93 %).…”

“…It is followed by carbopalladation (species B) then transmetalation In their recent contribution, compounds 24 b have been applied in carbamoyl-carbamoylation using Mo(CO) 6 as the carbonyl source. [115] A wide range of products were synthesized bearing amidated functions with the use of SPhos ligand and DBU (18 examples, 50-93 %). Varied oxindole derivatives were also generated under similar conditions in the presence of DABCO as base reacting alcohols or thiols (Scheme 86).…”

Palladium-Catalyzed Denitrogenative Carbonylation of Benzotriazoles with Cr(CO)6 as the Carbonyl Source

“…Among the various CO surrogates, metal–carbonyl complexes exhibit a broad application in transition-metal-catalyzed carbonylative reactions, which can in situ liberate CO gas via thermal decomposition or ligand-exchange processes . In 2002, Mo­(CO) 6 was first applied to the palladium-catalyzed aminocarbonylation of aryl bromides and iodides under microwave conditions by the group of Larhed and co-workers . Subsequently, much of the literature on carbonylation is extensive and focuses on using different metal–carbonyl complexes including Cr­(CO) 6 , W­(CO) 6 , Co 2 (CO) 8 , etc.…”