One-pot cross-metathesis/tandem carbonyl ylide formation-intramolecular cycloaddition of an unsaturated 2-diazo-3,6-diketoester.

Dicarbonyl-stabilised diazo functionality is tolerated during alkene cross-metathesis using Grubbs' catalyst, but undergoes subsequent tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition on addition of catalytic Rh2(OAc)4 in a one-pot operation.

Catalytic enantioselective intermolecular cycloadditions of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkene dipolarophiles.

Catalyzed cascade reactions that generate molecular complexity rapidly and in an enantioselective manner are attractive methods for asymmetric synthesis. In the present article, chiral rhodium catalysts are shown to effect such a transformation by using a range of 2-diazo-3,6-diketoesters with bicyclo[2.2.

The scope of catalytic enantioselective tandem carbonyl ylide formation-intramolecular [3 + 2] cycloadditions.

Catalytic enantioselective tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reactions of 2-diazo-3,6-diketoesters show promising scope in terms of asymmetric induction as the tethered alkene/alkyne dipolarophile component is varied. Cycloadditions were found to occur in moderate to very good yields, with a difference in ee exhibited by the electronically different 2-diazo-3,6-diketoesters 1, 25 and 33, 34. Values for ee of up to 90% for alkene dipolarophiles and up to 86% for alkyne dipolarophiles were obtained.