Synergistic Peptide and Gold Catalysis: Enantioselective Addition of Branched Aldehydes to Allenamides.

The combination of a peptide catalyst and a gold catalyst is presented for enantioselective addition reactions between branched aldehydes and allenamides. The two catalysts act in concert to provide γ,δ-enamide aldehydes bearing a fully substituted, benzylic stereogenic center - a structural motif common in many natural products and therapeutically active compounds - with good yields and enantioselectivities. The reaction tolerates a variety of alkyl and alkoxy substituted aldehydes and the products can be elaborated into several chiral building blocks bearing either 1,4- or 1,5- functional group relationships. Mechanistic studies showed that the conformational features of the peptide are important for both the catalytic efficiency and stereochemistry, while a balance of acid/base additives is key for ensuring formation of the desired product over undesired side reactions.

Enantioselective Synthesis of 1-Aryl Benzo[5]helicenes Using BINOL-Derived Cationic Phosphonites as Ancillary Ligands.

The synthesis of unprecedented BINOL-derived cationic phosphonites is described. Through the use of these phosphanes as ancillary ligands in AuI catalysis, a highly regio- and enantioselective assembly of appropriately designed alkynes into 1-(aryl)benzo[5]carbohelicenes is achieved. The modular synthesis of these ligands and the enhanced reactivity that they impart to AuI -centers after coordination have been found to be the key features that allow an optimization of the reaction conditions until the desired benzo[5]helicenes are obtained with high yield and enantioselectivity.

Orientation and conformation of two [6]carbohelicenes in stretched polystyrene and a thermoresponsive polyaspartate.

Two functionalized [6]carbohelicenes, one of which was also available in its two enantiomeric pure forms, were oriented in stretched polystyrene in CDCl3 , and in a recently introduced chiral thermoresponsive lyotropic polyaspartate (poly(benzyl)0.5 (phenethyl)0.5 -L-aspartate) in C2 D2 Cl4 . From the resulting 1 H,13 C residual dipolar couplings, the helical pitch of a methylated [6]carbohelicene was determined and found to be in agreement with theoretical predictions and existing crystal structures (d(C2,C2') ≈ 4.3 Å). For a second [6]carbohelicene with para-methoxyphenyl substituents, a clear conformational preference of the substituents was observed. The orientational properties of the two helicene enantiomers in the chiral polyaspartate are very similar, but both drastically change around 306 K. We suggest this behavior is due to an unusual phase transition in the liquid crystal.

Enantioselective Synthesis of [6]Carbohelicenes.

The use of α-cationic phosphonites derived from TADDOL as ancillary ligands has allowed a highly regio- and enantioselective synthesis of substituted [6]carbohelicenes by sequential Au-catalyzed intramolecular hydroarylation of diynes. Key for these results is the modular structure of these new ligands, and the enhanced reactivity that they impart to Au(I)-centers after coordination.