A facile route to polysubstituted 2-pyrones from readily available 2-acylcyclopropane-1-aryl-1-carboxylates mediated by TfOH is reported. The strongly donating 1-aryl group is important for directing the C–C bond cleavage of the donor-acceptor cyclopropane ring, which then leads to the formation of the 2-pyrone ring through lactonization.

Facile Synthesis of Polysubstituted 2-Pyrones via TfOH-Mediated Ring Expansion of 2-Acylcyclopropane-1-carboxylates

The importance of intramolecular constraints in cyclic transition-state geometries is especially pronounced in n-endo-tet cyclizations, where the usual backside approach of a nucleophile to the breaking bond is impossible for the rings containing less than eight atoms. Herein, we expand the limits of endo-tet cyclizations and show that donor-acceptor cyclopropanes can provide a seven-membered ring via a genuine 6-endo-tet process. Substrates containing a N-alkyl-N-arylcarbamoyl moiety as an acceptor group undergo Lewis acid-induced cyclization to form tetrahydrobenz[b]azepin-2-ones in high yields. The reaction proceeds with the inversion of the configuration at the electrophilic carbon. In this process, a formally six-membered transition state yields a seven-membered ring as the pre-existing cycle is merged into the forming ring. The stereochemistry of the products can be controlled by the reaction time and by the nature of Lewis acid, opening access to both diastereomers by tuning of the reaction conditions.

Expanding Stereoelectronic Limits of endo-tet Cyclizations: Synthesis of Benz[b]azepines from Donor-Acceptor Cyclopropanes.

Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans

Fusion of the cyclopropane ring bearing two vicinal acceptors to the pre-aromatic dihydrophenanthrene ring, which is constructed by the Pd-catalyzed cross-coupling between the vicinal aromatic rings, is found to effectively direct the cleavage of the electronically unfavored cyclopropane bond between the vicinal acceptors. Consequently, a modular method for the rapid synthesis of dibenzo[f,h]isocoumarins from methyl ketones, aryl aldehydes, and α-keto esters via a reaction cascade of aldol condensation, Kukhtin-Ramirez cyclopropanation, Pd-catalyzed direct arylation, and acid-promoted aromatization has been realized.

Tuning the Cyclopropane Ring-Opening Reaction over Electronic Bias by Fusion to a Pre-Aromatic Ring: TfOH-Promoted Aromatization of Dibenzonorcaradienes to Dibenzo[f,h]isocoumarins.

The chemistry of donor-acceptor (D-A) cyclopropanes containing alkyl donors has been scantily investigated. In the present work, we have synthesized new D-A cyclopropanes containing arylethyl donors and explored their reactivity in the presence of Lewis acids. Upon treatment with SnCl4, these cyclopropanes underwent the Cloke-Wilson rearrangement to yield 3,4,5-trisubstituted γ-butyrolactones in good yields with high diastereoselectivity.

The Cloke-Wilson rearrangement of aroyl-substituted donor-acceptor cylopropanes containing arylethyl donors.

Cooperation of Cis Vicinal Acceptors for Donor-Acceptor Cyclopropane Activation: TfOH-Promoted Ring-Opening/Aryl Shift Rearrangement to 3- and 5-Ylidenebutenolides.

Jiru Shao

Papers

Cooperation of Cis Vicinal Acceptors for Donor-Acceptor Cyclopropane Activation: TfOH-Promoted Ring-Opening/Aryl Shift Rearrangement to 3- and 5-Ylidenebutenolides.