A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclo[3.1.0]hexane Frameworks.

Yang, Zhen‐Hong; Chen, Peng; Chen, Zhi‐Chao; Chen, Zhi; Du, Wei; Chen, Ying‐Chun

Here we report that the chemoselective activation of Tsuji's 2‐(cyanomethyl)allyl carbonates to generate the palladium–trimethylenemethane 1,3‐dipoles via a deprotonation strategy can be realized in the presence of Morita–Baylis–Hillman carbonates from substantial activated ketones. The following SN2′‐addition enables the formation of new 1,3‐dipole species having an activated alkene moiety through a second deprotonation process, which then undergo cascade [1 2]/[3 2] annulations to furnish complex bicyclic [3.1.0]hexane frameworks having three contiguous quaternary stereogenic centers with good to excellent enantioselectivity. Moreover, by using benzoyl aldehyde‐derived substrates, a [1 4]/[3 2] annulation sequence is similarly developed to produce fused cyclopenta[b]furan architectures.

PROTON transfer reactions; ANNULATION; HEXANE; CARBONATES; KETONES; CARBONATE minerals; FURANS synthesis

Angewandte Chemie, 2021, Vol 133, Issue 25, p14032

0044-8249

Academic Journal

10.1002/ange.202102842