New Methods for the Formation of Carbon-Carbon Bonds from Alcohols

The development of new methods for the formation of carbon-carbon bonds is a cornerstone of organic chemistry and especially the valorization of sustainable feedstocks, containing for example alcohol functionalities, is of great interest.
Chapter 2 describes the development of a novel method for the selective synthesis of (E)-stilbenes from benzylic alcohols. This was initially achieved by a potassium tertbutoxide mediated coupling of arylacetonitriles and benzylic alcohols. The reaction was then expanded to a two-step one-pot procedure enabling the synthesis of stilbenes starting from benzylic chlorides. Mechanistic investigations revealed that the reaction most likely proceeds via a Meerwein-Ponndorf-Verley reduction/Oppenauer oxidation type alkylation followed by an E1cB elimination of cyanide to afford stilbene.
Chapter 3 summarizes the investigations into the valorization of ethylene glycol, as a potentially biomass derived compound, employing photoredox catalysis. Carbon-carbon bond formation to electron-deficient olefins could be achieved using an iridium based photocatalyst in addition to quinuclidine as a co-catalyst and methyl boronic acid as a C-H bond weakening catalyst.
Chapter 4 describes a study of the recently proposed nonclassical benzene bioisostere
2-oxabicyclo[2.2.2]octane (oxaBCO), conducted during the external research stay at Lundbeck. Analogues of Resveratrol, Benzocaine, and Leteprinim containing the BCO or oxaBCO motif were synthesized, which should be investigated for their physicochemical properties to gain further information of the potential utility of oxaBCO as a bioisostere of the para-substituted benzene ring.