Cyclopropanation Strategies in Recent Total Syntheses

2017/05/03 by Christian Ebner, Erick M. Carreira · 30 citations
Chemistry · #Cyclopropane Reaction Mechanisms #Catalytic Alkyne Reactions #Asymmetric Synthesis and Catalysis

paper · doi:10.1021/acs.chemrev.6b00798

Abstract

Complex molecular architectures containing cyclopropanes present significant challenges for any synthetic chemist. This review aims to highlight the strategic considerations for introduction of the cyclopropane motif in a collection of recent total syntheses. At first, an overview of the most important and widely used cyclopropanation techniques is presented, followed by a discussion of elegant approaches and clever solutions that have been developed to enable the synthesis of various unique cyclopropane natural products or use of cyclopropanes as versatile strategic intermediates.

Citations

• Biosynthesis and Metabolism of Cyclopropane Rings in Natural Compounds

Cited by

• Deuterated Cyclopropanation of Alkenes by Iron Catalysis
• Copper-catalyzed aerobic oxyalkylation of alkenes with cyclopropanols: A straightforward access to 1,5-diketones
• Control of adjacent S(IV) and spiro stereocenters via Pd-catalyzed asymmetric (3+2) cyclization
• Selective Carbon–Carbon Bond Cleavage of Cyclopropanols
• Biosynthesis of cyclopropane in natural products
• Cyclopropanations via Heme Carbenes: Basic Mechanism and Effects of Carbene Substituent, Protein Axial Ligand, and Porphyrin Substitution. [europepmc]
• Radical asymmetric intramolecular α-cyclopropanation of aldehydes towards bicyclo[3.1.0]hexanes containing vicinal all-carbon quaternary stereocenters. [europepmc]
• Redox-Neutral Photocatalytic Cyclopropanation via Radical/Polar Crossover. [europepmc]
• A radical S-adenosyl-L-methionine enzyme and a methyltransferase catalyze cyclopropane formation in natural product biosynthesis. [europepmc]
• Stereodivergent Rhodium(III)-Catalyzed cis-Cyclopropanation Enabled by Multivariate Optimization. [europepmc]
• Efficient and stereodivergent synthesis of unsaturated acyclic fragments bearing contiguous stereogenic elements. [europepmc]
• Chiral cyclopentadienyl Rh III -catalyzed enantioselective cyclopropanation of electron-deficient olefins enable rapid access to UPF-648 and oxylipin natural products. [europepmc]
• Rh(III)-Catalyzed C-H Activation-Initiated Directed Cyclopropanation of Allylic Alcohols. [europepmc]
• Photoredox-catalyzed oxo-amination of aryl cyclopropanes. [europepmc]
• α-Imino Gold Carbene Intermediates from Readily Accessible Sulfilimines: Intermolecular Access to Structural Diversity. [europepmc]
• Nickel-Catalyzed Alkyl-Alkyl Cross-Electrophile Coupling Reaction of 1,3-Dimesylates for the Synthesis of Alkylcyclopropanes. [europepmc]
• Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes. [europepmc]
• Stereoselective Cyclopropanation of Electron-Deficient Olefins with a Cofactor Redesigned Carbene Transferase Featuring Radical Reactivity. [europepmc]
• Transient-axial-chirality controlled asymmetric rhodium-carbene C(sp 2 )-H functionalization for the synthesis of chiral fluorenes. [europepmc]
• Asymmetric Catalysis Mediated by Synthetic Peptides, Version 2.0: Expansion of Scope and Mechanisms. [europepmc]
• Gold-Catalyzed Synthesis of Small Rings. [europepmc]
• Catalytic Cyclopropanol Ring Opening for Divergent Syntheses of γ-Butyrolactones and δ-Ketoesters Containing All-Carbon Quaternary Centers. [europepmc]
• Visible Light Induced Brønsted Acid Assisted Pd-Catalyzed Alkyl Heck Reaction of Diazo Compounds and N-Tosylhydrazones. [europepmc]
• Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes. [europepmc]
• Control of Redox-Active Ester Reactivity Enables a General Cross-Electrophile Approach to Access Arylated Strained Rings. [europepmc]
• Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes. [europepmc]
• Intermolecular Organophotocatalytic Cyclopropanation of Unactivated Olefins. [europepmc]
• Design of Heme Enzymes with a Tunable Substrate Binding Pocket Adjacent to an Open Metal Coordination Site. [europepmc]
• Photosensitized O 2 enables intermolecular alkene cyclopropanation by active methylene compounds. [europepmc]
• Visible Light-Induced Reactions of Diazo Compounds and Their Precursors. [europepmc]

Related

• Recent Progresses towards the Strengthening of Cyclopropene Chemistry
• Catalytic Enantioselective Ring-Opening Reactions of Cyclopropanes
• Biosynthesis of cyclopropane in natural products
• Selective Carbon–Carbon Bond Cleavage of Cyclopropanols
• Recent Synthetic Strategies to Access Seven-Membered Carbocycles in Natural Product Synthesis