Department of Medicinal and Organic Chemistry, School of Pharmacy, Iwate Medical University, Yahaba,Iwate 028-3694, Japan.
J Org Chem. 2009 Dec 18;74(24):9274-9. doi: 10.1021/jo901778a.
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.
通过钯催化的分子内氧化氨羰基化反应，描述了四氢吡咯并[1,2-c]嘧啶-1,3-二酮的对映选择性合成。烯基脲底物的碳-碳双键在一氧化碳气氛下，在钯催化剂的存在下，与氮亲核试剂进行分子内反应。使用手性螺双（异恶唑啉）配体（SPRIX）对于获得所需的光学活性形式的产物是必不可少的。与其他已知配体的配位能力相比，SPRIX 的这种特殊性质源于两个结构特征：异恶唑啉配位位点的低sigma-给体能力和螺骨架的刚性。
