The Bellus-Claisen rearrangement.

Among the reactions available to synthetic chemists for the construction of new C--C bonds, the Claisen rearrangement is one of the most powerful, elegant, and well-characterized methods. A genuinely new variant, the Bellus-Claisen rearrangement came to light a quarter of a century ago: The reaction of an allylic ether, thioether, or amine with a ketene leads through a [3,3] sigmatropic bond reorganization of a zwitterionic intermediate to an E unsaturated ester, thioester, or amide. When applied to cyclic allylic substrates, a ring-enlargement by four carbon atoms in one step provides medium-ring unsaturated E-configured lactones, thiolactones, and lactams. The scope of the Bellus-Claisen rearrangement and the optimum reaction conditions will be discussed in this Minireview.