Enantioselective Palladium-Catalyzed [3C + 2C] and [4C + 3C] Intramolecular Cycloadditions of Alkylidenecyclopropanes

Abstract

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Recent Advances in Transition-Metal-Catalyzed (4+3)-Cycloadditions

“…56 The authors recently demonstrated the Pd-catalyzed formation of desirable 5,7-and 5-5-bicyclic systems 4.3b/4.3c from simple diene-tethered alkylidenecyclopropanes 4.3a in good yields and enantioselectivities using Feringa's phosphoramidite ligand (Scheme 4.3a). 56,57 Interestingly, the (S,R,R)-ligand gave better enantioselectivities and higher selectivity for the (4+3)-cycloadduct over the (3+2)-cycloadduct compared to when the (R,R,R)-ligand was used. The authors propose that the Pd-catalyst oxidatively adds into the cyclopropane ring at the distal bond to form a metallocyclobutane 4.3d (Scheme 4.3b).…”

Catalytic Domino Annulations through η3‐Allylpalladium Chemistry: A Never‐Ending Story

“…An enantioselective version of the above [3+2]-cycloaddition has been later reported by the same group starting from unsaturated ACPs. [83] The best results were obtained by using the bulky phosphoramidite ligand (S,R,R)-L10 (Scheme 41). When the dipolarophile bears a conjugated diene instead of an electron-poor alkene, the [4+3]-cycloaddition is the favored over the [3+2].…”

“…An enantioselective version of the above [3+2]‐cycloaddition has been later reported by the same group starting from unsaturated ACPs . The best results were obtained by using the bulky phosphoramidite ligand ( S , R , R )‐ L10 (Scheme ).…”

Construction of Carbocycles from Methylenecyclopropanes

“…The reaction was then successfully employed in a total synthesis of pyrovellerolactone . Similarly, Pd‐catalyzed intramolecular cyclizations of MCP‐containing molecules to synthesize the heterocycle‐fused cycloheptenes were also achieved …”