The synthesis and characterization of organic compounds with unusual atom or functional group connectivity is one of the main driving forces in the discovery of new synthetic methods that has raised the interest of chemists for many years. Polycarbonyl compounds are such compounds wherein multiple carbonyl groups are directly juxtaposed and influence each other’s chemical reactivity. While 1,2-dicarbonyl or 1,2,3-tricarbonyl compounds are well-known in organic chemistry, the 1,2,3,4-tetracarbonyl motif remains barely explored. Herein, we report on the synthesis of such 1,2,3,4-tetracarbonyl compounds employing a synthetic strategy that involves C-nitrosation of enoldiazoacetates, while the diazo functional group remains untouched. This strategy not only leverages the synthesis of 1,2,3,4-tetracarbonyl compounds to an unprecedented level, it also accomplishes the synthesis of 1,2,3,4-tetracarbonyl compounds, wherein each carbonyl group is orthogonally masked. Combined experimental and theoretical studies provide an understanding of the reaction mechanism and rationalize the formation of such 1,2,3,4-tetracarbonyl compounds.

具有不寻常原子或官能团连通性的有机化合物的合成和表征是发现新合成方法的主要驱动力之一，多年来引起了化学家的兴趣。多羰基化合物是这样的化合物，其中多个羰基直接并列并影响彼此的化学反应性。虽然 1,2-二羰基或 1,2,3-三羰基化合物在有机化学中广为人知，但 1,2,3,4-四羰基基序仍鲜有探索。在此，我们报告了此类 1,2,3,4-四羰基化合物的合成，采用的合成策略涉及烯醇重氮乙酸酯的 C-亚硝化，而重氮官能团保持不变。该策略不仅将 1,2,3,4-四羰基化合物的合成利用到了前所未有的水平，它还完成了1,2,3,4-四羰基化合物的合成，其中每个羰基都是正交掩蔽的。结合实验和理论研究提供了对反应机制的理解，并使此类 1,2,3,4-四羰基化合物的形成合理化。