Enantioselective intramolecular oxidative aminocarbonylation of alkenylureas catalyzed by palladium-spiro bis(isoxazoline) complexes.
An enantioselective synthesis of tetrahydropyrrolo[1,2-c]pyrimidine-1,3-diones via a palladium-catalyzed intramolecular oxidative aminocarbonylation is described. The carbon-carbon double bond of alkenylurea substrates has been shown to react intramolecularly with a nitrogen nucleophile in the presence of a palladium catalyst under a carbon monoxide atmosphere. The use of a chiral spiro bis(isoxazoline) ligand (SPRIX) is essential to obtain the desired products in optically active forms. In comparison with the coordination ability of other known ligands, this peculiar character of SPRIX originates from two structural characteristics: low sigma-donor ability of the isoxazoline coordination site and rigidity of the spiro skeleton.
Tsujihara
Tetsuya
T
Department of Medicinal and Organic Chemistry, School of Pharmacy, Iwate Medical University, Yahaba,Iwate 028-3694, Japan.
Shinohara
Toshio
T
Takenaka
Kazuhiro
K
Takizawa
Shinobu
S
Onitsuka
Kiyotaka
K
Hatanaka
Minoru
M
Sasai
Hiroaki
H
D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D007555:Isoxazoles / Q000737:chemistry*; D008024:Ligands; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D011743:Pyrimidines / Q000138:chemical synthesis / Q000737:chemistry; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry; D013141:Spiro Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D014508:Urea / Q000031:analogs & derivatives* / Q000737:chemistry*
D000475:Alkenes; D007555:Isoxazoles; D008024:Ligands; D009942:Organometallic Compounds; D011743:Pyrimidines; D011758:Pyrroles; D013141:Spiro Compounds; C547268:tetrahydropyrrolo(1,2-c)pyrimidine-1,3-dione; D010165:Palladium; D014508:Urea