Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Abstract

The carbon–carbon (C–C) bond cleavage of cyclopropanols is a wide area of research with much current activity. This review highlights new developments in this area over the past two decades. A summary is made of the three main reactivity modes, namely, homoenolate chemistry, β-keto radical chemistry, and acid-catalyzed ring-opening, as well as all other methods for the C–C bond cleavage and functionalization of cyclopropanols, including base-mediated ring-opening, metal-catalyzed C–C insertions and eliminations, oxidative fragmentation using hypervalent iodine reagents, reactions of donor–acceptor cyclopropanols, and pericylic reactions. Emphasis is placed on the synthetic utility of cyclopropanols and related derivatives, which have emerged as unique three-carbon synthons.

Enantioselective palladium-catalyzed C(sp2)–C(sp2) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones

“…Accordingly, the construction and breaking of carbon-carbon bonds is one of the most important research topics in modern synthetic chemistry and has been attracted much attentions by chemists in the past decades. [1][2][3][4][5][6][7][8][9][10][11] Despite numerous new reaction strategies have been developed, the improvement of adaptability of catalyst or reaction systems through carbon-carbon bond activation for the enantioselective construction of chiral molecules with complex structures are still not an easy task. In addition, carbon-carbon bond activation of small rings for the synthesis and functionalization of cyclic compounds is intrinsically challenging to a variety of synthetic chemistry and pharmaceutical application.…”

“…To address current limitations on the enantioselective and rarely reported transition-metal-catalyzed (3+2) spiro-annulation of cyclopropenones with ketones, we expect to design rigid and cyclic diketone substrates to realize a new strategy of constructing two vicinal carbon quaternary stereocenters based on C(sp 2 )-C(sp 2 ) bond activation and desymmetrization that similarly to atom-economic (3+2) click additions 70 . However, the utilization and re-organization of two small rings in transition-metal-catalyzed (3+2) spiroannulation to create oxaspiro cyclopentenone-lactone scaffolds remains elusive.…”

Generation of Mixed Anhydrides via Oxidative Fragmentation of Tertiary Cyclopropanols with Phenyliodine(III) Dicarboxylates

“…Currently, hydroxy-substituted cyclopropanes (cyclopropanols) are widely used in organic synthesis as versatile C 3 -building blocks [1][2][3][4][5], with a rapidly growing number of novel applications [6,7]. The remarkable progress in the field has been largely driven by the two following reasons.…”

Reversible C–C Bond Formation Using Palladium Catalysis

“…The most prevalent β-carbon eliminations are driven by release of ring strain. [16][17][18][19][20] The most common examples of this are when cyclic alcohols are used to form metal homoenolate nucleophiles (Scheme 1a). 16 The relief of steric strain via a β-carbon elimination, as seen in the Catellani reaction, rely on the build-up of increasing steric encumbrance during the course of the reaction (Scheme 1b).…”

“…[16][17][18][19][20] The most common examples of this are when cyclic alcohols are used to form metal homoenolate nucleophiles (Scheme 1a). 16 The relief of steric strain via a β-carbon elimination, as seen in the Catellani reaction, rely on the build-up of increasing steric encumbrance during the course of the reaction (Scheme 1b). 17,21,22 Other strategies to enable β-carbon eliminations rely on the formation of a strong π-bond (Scheme 1c).…”