Catalyzed addition of diazoacetoacetates to imines: synthesis of highly functionalized aziridines

Abstract

The addition of diazoacetoacetates to aromatic imines derived from p-methoxyaniline is achieved using dirhodium tetraacetate as the catalyst. Highly functionalized aziridines are obtained in good yield and with excellent stereoselectivity. 2-Diazo-1,3-diketones also provide good yields of aziridines, but dimethyl diazomalonate is inactive in the transformation. The diazoacetoacetates of chiral alcohols are also examined in the reaction and moderate diastereoselectivity is achieved with (R)-pantolactone-derived diazoacetoacetate. A reaction mechanism through metal-carbene and azomethine ylide is proposed.

Chiral Dirhodium(II) Carboxylates: New Insights into the Effect of Ligand Stereo-Purity on Catalyst Structure and Enantioselectivity

“…Chiral dirhodium(II) complexes are currently renowned as catalysts that can effectively drive a broad spectrum of reactions with superior levels of chemo-, regio-and stereo-selectivity [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Their remarkable selectivity has reached a stage where they can function as powerful tools in building up value added molecules with complex structures [7,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”

ChemInform Abstract: Highly Efficient Asymmetric Aziridination of Unsaturated Aldehydes Promoted by Chiral Hetero‐Organic Catalysts.

“…[2][3][4] Chiral aziridines constitute av ery useful group of synthetic intermediates for the synthesis of amino acids, natural products, and pharmaceuticals. [5][6][7][8] The basic reactionf or the construction of such chiral heterocycles with at hree-membered ring is asymmetric aziridination, [9,10] which can generally be conducted using chiral auxiliaries [11][12][13][14][15] or chiral catalysts. [16][17][18][19][20] This kind of asymmetric transformation often constitutes one step in the synthetic pathway of many natural and biologically active compounds, for example, sphinganines.…”

Highly Efficient Asymmetric Aziridination of Unsaturated Aldehydes Promoted by Chiral Hetero‐organic Catalysts

“…Chiral aziridines constitute a very useful group of synthetic intermediates for the synthesis of amino acids, natural products, and pharmaceuticals . The basic reaction for the construction of such chiral heterocycles with a three‐membered ring is asymmetric aziridination, which can generally be conducted using chiral auxiliaries or chiral catalysts . This kind of asymmetric transformation often constitutes one step in the synthetic pathway of many natural and biologically active compounds, for example, sphinganines …”