# Comparison of metal-carbenoid reactions of β-2-five-membered heteroaryl substituted α,β-unsaturated ketones

## TL;DR

This paper compares how different catalysts and ketone structures affect the outcomes of metal-carbenoid reactions.

## Contribution

The study reveals distinct product formations based on ketone substitution and diazo compound characteristics.

## Key findings

- N-methyl 2-pyrrolyl ketones mainly form insertion derivatives.
- 2-thiophenyl and 2-furyl ketones with dimethyl diazomalonate yield dihydrofuran products.
- 1-diazo-1-phenyl-propane-2-one produces 1-phenylpropane-1,2-dione with specific ketones.

## Abstract

In this study, β-2-heteroaryl substituted (N-methyl 2-pyrrolyl, 2-thiophenyl, 2-furyl) α,β-unsaturated ketones were reacted with two α-diazo carbonyl compounds that had different characteristics (dimethyl diazo malonate and 1-diazo-1-phenyl-propane-2-one) in the presence of both copper and rhodium catalysts. In the case of reactions with N-methyl 2-pyrrolyl α,β-unsaturated ketones, the major product was the insertion derivative. However, in the reactions of 2-thiophenyl and 2-furyl α,β-unsaturated ketones with dimethyl diazomalonate (acceptor-acceptor disubstituted), only dihydrofuran products were formed over carbonyl ylides. When 2-thiophenyl and 2-furyl α,β-unsaturated ketones were reacted with 1-diazo-1-phenyl-propane-2-one (donor-acceptor disubstituted), 1-phenylpropane-1,2-dione was obtained under our reaction conditions.