Discovery and synthesis of atropisomerically chiral acyl-substituted stable vinyl sulfoxonium ylides.

Atropisomerism is a type of conformational chirality that plays a critical role in various fields of chemistry, including synthetic, medicinal and material chemistry, and its impact has been widely recognized. Although chiral atropisomerism in rotationally restricted aryl-aryl bonds has garnered substantial interest and led to important discoveries in chiral catalysts and drug development, the exploration of non-aryl atropisomers has fallen behind. Here we reveal a previously unexplored form of non-aryl atropisomerism by linking a sterically congested olefin to a sulfoxonium ylide.

Direct Synthesis of Bicyclic Acetals via Visible Light Catalysis.

Polysubstituted bicyclic acetals are a class of privileged pharmacophores with a unique 3D structure and an adjacent pair of hydrogen bond acceptors. The key, fused acetal functionality is often assembled, via intramolecular cyclization, from linear substrates that are not readily available. Herein, we report a formal cycloaddition between cinnamyl alcohols and cyclic enol ethers under ambient photoredox catalysis conditions.

Direct Synthesis of Polysubstituted Aldehydes via Visible-Light Catalysis.

Aldehydes are among the most versatile functional groups for synthetic chemistry. However, access to polysubstituted alkyl aldehydes is very limited and requires lengthy synthetic routes that involve multiple-step functional-group conversion. This paper reports a one-step synthesis of polysubstituted aldehydes from readily available olefin substrates using visible-light photoredox catalysis.

Pd-Catalyzed Cross-Coupling of Terminal Alkynes with Chromium(0) Fischer Carbene Complexes.

Alkyl chromium(0) carbene complexes typically undergo cycloadditions with alkynes to afford carbo- or heterocyclic compounds. In the presence of Pd catalyst, it is demonstrated that a traditional cycloaddition pathway is completely altered: instead of cycloaddition, oxidative cross-coupling reaction of alkyl chromium(0) carbene complexes with terminal alkynes occurs. The coupling reaction exhibits excellent functional group tolerance and good efficiency.

Visible-Light-Mediated [4+2] Cycloaddition of Styrenes: Synthesis of Tetralin Derivatives.

We report a formal [4+2] cycloaddition reaction of styrenes under visible-light catalysis. Two styrene molecules with different electronic or steric properties were found to react with each other in good yield and excellent chemo- and regioselectivity. This reaction provides direct access to polysubstituted tetralin scaffolds from readily available styrenes.