Julia-Kocienski olefination reaction

Plesniak K, Zarecki A, Wicha J (2007) The Smiles Rearrangement and the Julia-Kocienski Olefination Reaction. 275 163-250 Polito M, see Braga D (2005) 254 71-94 Poulin-Kerstien AT, see Dervan PB (2005) 253 1-31... 

The Smiles Rearrangement and the Julia-Kocienski Olefination Reaction... 

In a pivotal modification of the direct olefination reaction Kocienski and his coworkers [10] showed that the use of l-phenyl-lff-tetrazol-5-yl sulfones, preferentially with NaHMDS or KHMDS as the base and DME as the solvent, provides olefins in excellent yields and stereoselectivity with respect to -isomers. The modified version of the direct olefination reaction has frequently been referred to as the Julia-Kocienski olefination reaction. 

Table 10 Heterocyclic and aromatic sulfones used in the Julia-Kocienski olefination reaction ...

In the synthesis of novel antifimgal agent Ambruticin by Jacobsen and coworkers [114] the major building blocks were connected using the Julia-Kocienski olefination reaction (Scheme 87). It was found that high selectivity for either double bond isomer could be obtained NaHMDS in THF providing Z alkene (Table 24, entries 1 and 2) whereas LHMDS in polar solvents afforded the desired E isomer almost exclusively (entries 3 and 4). 

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