Weak Nucleophiles in the Aza‐Michael Reaction

Abstract

The 1,4‐conjugated addition of nitrogen centered nucleophiles to electron‐deficient alkenes is one of the most significant and widely used reactions in modern synthetic organic chemistry. To date, various protocols for the aza‐Michael reaction have been developed. However, these reports mainly focus on the use of strong Michael donors. In recent years, the conjugate addition of weak nitrogen nucleophiles to various Michael acceptors gained increasing popularity. Impressive progress in this area has been achieved by the use of more efficient catalyst systems. This review aims to provide a critical analysis of the results obtained in reactions of weak nucleophiles (azoles, pyrroles, indoles, carbamates, purines, amides, hydrazides, uraciles etc) with electron‐deficient alkenes which were reported over the past twelve years.

Aza‐Michael Reaction: A Decade Later – Is the Research Over?

“…The progress made in the field of conjugate nucleophilic addition during last decade is impressive, but there is still much work to be done on the research of the aza-Michael reaction, namely the design and application of more efficient and recyclable catalysts, introduction of poor nucleophiles into conjugate nucleophilic addition (for very recent review about a participation of weak nucleophiles in the aza-Michael reaction, see Ref. [213]), development of chemo-, regio-and stereoselective methods for the synthesis of valuable nitrogenbearing linear and heterocyclic compounds. The only answer to the question in the title of the review should be as following: no, research is not over.…”

New Functional Alkoxysilanes and Silatranes: Synthesis, Structure, Properties, and Possible Applications

“…Among nucleophilic addition processes, the aza-Michael reaction holds a special place [ 22 , 23 , 24 ]. This general reaction proceeds with the participation of various Michael donors (carbamates, amides, amines) and Michael acceptors (unsaturated nitriles, sulfones, phosphonates, and also acrylates).…”

Hydrazine Hydrate in Asymmetric Synthesis: A Bifunctional Squaramide Catalytic Approach toward Fused Pyrazolines

“…This observation could be tied to the faster rate of cyclization once hydrazone formed. Based on literature precedent , and the chiral squaramide-catalyzed , aza-Michael addition reactions, the possible bifunctional transition states depicted in Scheme help to shed light on the observed absolute stereochemical outcome. In this model, one of the enones involved in hydrogen-bonding interactions with the squaramide part of the catalyst and the NH 2 of the in situ formed hydrazone of other enone interacts with the tertiary amine counterpart.…”