Catalytic Enantioselective Ring-Opening Reactions of Cyclopropanes

Abstract

This review describes the development of enantioselective methods for the ring opening of cyclopropanes. Both approaches based on the reaction of nonchiral cyclopropanes and (dynamic) kinetic resolutions and asymmetric transformations of chiral substrates are presented. The review is organized according to substrate classes, starting by the more mature field of donor−acceptor cyclopropanes. Emerging methods for enantioselective ring opening of acceptor-or donor-only cyclopropanes are then presented. The last part of the review describes the ring opening of more reactive three-membered rings substituted with unsaturations with a particular focus on vinylcyclopropanes, alkylidenecyclopropanes, and vinylidenecyclopropanes. In the last two decades, the field has grown from a proof of concept stage to a broad range of methods for accessing enantioenriched building blocks, and further extensive developments can be expected in the future.

Rhodium-catalysed selective C–C bond activation and borylation of cyclopropanes

“… 11 In this context, they have been exploited as robust building blocks in organic synthesis, including C–H and C–C bond functionalizations. 12 Seminal work by Itami and Yamaguchi described the N -Piv-directed C–H borylation of CPAs with cis selectivity using phenanthroline-based ligands and a catalytic amount of an iridium salt ( Fig. 1B ).…”

Merging C–H and C–C Activation in Pd(II)-Catalyzed Enantioselective Synthesis of Axially Chiral Biaryls

“…[20][21][22] Three-membered cyclopropane motifs, a class of useful synthetic entities, are well-known applicable building blocks for C-C bond activation. [23][24][25] Since 2010, cyclopropanes, such as vinylcyclopropanes (VCPs) 26,27 and cyclopropanols, 28,29 have emerged as versatile synthons for C-H/C-C activation reactions. Generally, two different strategies based on the pathways of C-C cleavage in the catalytic system could be expected for the activation of cyclopropanes.…”

Regiodivergent Access to 2- or 3-Substituted Indanones: Catalyst-Controlled Carboacylation via C–C Bond Activation

“…Such carboacylation reactions have been extensively demonstrated in strained ring systems. [21][22][23][24][25][26] However, there are only a few known examples of unstrained systems, such as those reported by Douglas and Dong, and the regioselectivity of this reaction remains largely unexplored. [27][28][29][30] Motivated by the importance of directly forming indane rings, we envisioned using ketones as aldehyde surrogates in catalytic C-C activation.…”