alternate pathway consists of the formation of the benzylboronic acid via a zwitterionic intermediate, followed by protodeboronation of the benzylboronic acid under basic conditions, which results in the final reductive product. This methodology has also been extended to heteroatom nucleophiles to produce ethers and thioethers. A tandem rhodium-catalyzed Bamford-Stevens/thermal aliphatic Claisen rearrangement A novel process was developed by Stoltz in which the Bamford–Stevens reaction was combined with the Claisen rearrangement to produce a variety of olefin products. This transformation proceeds first by the thermal decomposition of N-aziridinylhydrazones to form the diazo compound (1), followed by a rhodium-mediated de-diazotization (2) and the syn 1,2-hydride shift (3). This substrate undergoes a thermal aliphatic Claisen rearrangement (4) to yield the product. Application to total synthesis Trost et al. utilized the Bamford–Stevens reaction in their total synthesis of (–)-isoclavukerin to introduce a diene moiety found in the natural product. A bicyclic trisylhydrazone was initially subjected to Shapiro reaction conditions (alkyllithiums or LDA), which only led to uncharacterizable decomposition products. When this bicyclic trisylhydrazone was subjected to strong base (KH) and heat, however, the desired diene product was generated. Moreover, it was shown that olefin generation and the following decarboxylation could be performed in one pot. To that end, excess NaI was added, along with an elevation in temperature to facilitate the Krapcho decarboxylation. References See also Shapiro reaction Olefination reactions Elimination reactions Name reactions