6.9 C–C Bond Formation: (aza) Morita–Baylis–Hillman Reaction

Abstract

The past 10 years have witnessed a rapid growth in the enantioselective and catalytic Morita–Baylis–Hillman (MBH) reactions. This efficient and atom-economic process, combined with other transformations, provides facile access to very complex molecules and finds wide applications in organic synthesis. The recent achievements in enantioselective MBH reactions coincided with the emergence of the concept of acid–base organocatalysis. The synergistic cooperation of acid–base functionalities in the catalytic site not only increases the chemical reactivity of substrates but also organizes the three-dimensional structure of the transition state for achieving high chemical yields and high enantioselectivities. To date, the MBH reaction is among the very few reactions wherein chiral organocatalysts yield better results than metal-based chiral catalysts. In this chapter, we have described recent mechanistic insights and advances in the enantioselective MBH and aza-MBH reactions.