A General Synthetic Strategy toward the Truxillate Natural Products via Solid-State Photocycloadditions.

The truxillates constitute a large class of dimeric natural products featuring a central, highly substituted cyclobutane core. In principle, these structures could be efficiently synthesized via [2 + 2] photocycloaddition. However, the difficulty in controlling the high-energy electronically excited reactive intermediates in the solution state can lead to poor regio- and diastereocontrol. This has limited the use of photocycloaddition methodology toward the synthesis of this important class of natural products. Herein, we demonstrate that acid-controlled precipitation of C-acyl imidazoles promotes a highly selective solid-state photocycloaddition, and the products of this reaction can be quickly transformed into truxillate natural products.

Allylic Amination of Highly Substituted Alkenes Enabled by Photoredox Catalysis and Cu(II)-Mediated Radical-Polar Crossover.

Allylic amination reactions enable the conversion of alkene feedstocks into value-added products with significant synthetic versatility. Here we describe a method for allylic amination involving photoredox activation and Cu(II)-mediated radical-polar crossover. A range of structurally varied allylic amines can be accessed using this strategy. The regioselectivity of this process is complementary to those of conventional methods for allylic amination.