Recent advances in the catalytic cyclopropanation of unsaturated compounds with diazomethane

Abstract

The main achievements and development trends of the past 10–15 years related to the catalytic cyclopropanation of unsaturated compounds with diazomethane are integrated and analyzed. The attention is focused on the most efficient catalysts based on palladium compounds. Data on the effects of substrate structure and nature of catalyst components on the regio- and stereoselectivity of these reactions are systematized. Characteristic features of safe methods for diazomethane generation are considered, including the use of membrane technologies and continuous-flow and in situ preparation methods, which have prospects for industrial application. The bibliography includes 281 references.

Unveiling the beauty of cyclopropane formation: a comprehensive survey of enantioselective Michael initiated ring closure (MIRC) reactions

“…Although previous reviews have covered cyclopropanation reactions, 17–38 there is currently no comprehensive account solely focused on Michael Initiated Ring Closure (MIRC) cyclopropanation. Therefore, we present a detailed account on enantioselective cyclopropanation, serving as a valuable resource for synthetic organic and medicinal chemists.…”

Pd/C catalytic cyclopropanation of polycyclic olefins for synthesis of high‐energy‐density strained fuels

“…And compounds incorporating cyclopropane moiety have been discovered in bioactive molecules, secondary metabolites and more than 4000 natural products. [1][2][3] Building the smallest carbocycle in molecules can induce some unique features stemmed from the shortened and bent C C bonds, constrained bond angle and resembled C C character different from conventional paraffines. 4 Especially, the unique properties of cyclopropane motif have attracted great interest in its utilization in liquid high-energy-density (HED) fuels, and a lot of cyclopropane-based fuels have been developed in recent years, which show much higher density and more energy content than conventional fuels.…”

“…Cyclopropane, the smallest cycloalkane ring, is a versatile building block in organic chemistry. And compounds incorporating cyclopropane moiety have been discovered in bioactive molecules, secondary metabolites and more than 4000 natural products 1–3 . Building the smallest carbocycle in molecules can induce some unique features stemmed from the shortened and bent CC bonds, constrained bond angle and resembled CC character different from conventional paraffines 4 .…”

Mixed‐Ligand Mandelato‐Phosphine Copper(I) Complexes as Active Catalysts in Carbene Transfer Reactions

“…Among the most convenient methods for the preparation of cyclopropane rings, transition‐metal‐catalyzed transfer reactions of carbenes to unsaturated organic compounds are one of the most efficient way, exploiting diazo compounds as carbene sources, [19] especially diazo acetates [20] because of their relatively higher stability and safety among the diazo compounds. These reactions are usually promoted by several metals, like rhodium, [21] ruthenium, [22] gold, [23] or copper, [24,25] the latter representing a very valid choice because of its low‐cost.…”