Julia, Marc

J. Simonet, unpublished observations concerning many aryl/alkyl sulphones provided by Prof. Marc Julia, Paris. 

Submitted by Marc Julia and Michel Malmy1 Checked bv Edward J. Zaiko and Herbert 0. House... 

A review of Mechanismes Electroniques en Chimie Organique. Augmented 2nd Edition by Marc Julia. R. U. Lemieux, J. Am. Chem. 

The fact that the Julia-Lythgoe olefination requires more than one step to prepare alkenes has generally been accepted as an inconvenient and inevitable part of the procedure developed by Marc Julia and Basil Lythgoe. This flaw kept nagging at Marc Julia s brother Sylvestre, who would not rest until he had found the one-step (Sylvestre) Julia olefination. The (Sylvestre) Julia-Kocienski olefination has become the state-of-the-art-variant of this olefination (Figure 11.23). It may be applied to any kind of aldehyde. 

Marc) Julia-Lythgoe- and (Sylvestre) Julia-Kocienski Olefination... 

Recent developments emphasise the convenience of replacing the three step (Marc) Julia reaction by one-step procedures using reagents 147 in which Ar is a heterocycle. Thus (Sylvestre) Julia used a benzothiazole 157. The adduct 158 with an aldehyde decomposes by fragmentation of the spiro compound 159 without the need for any further reagents to give S02, the alkene 150 and the benzothiazole 169. The benzene rings are omitted from 158-160 for clarity.31... 

Marc Julia (1922-2010) was born in Paris, did his PhD at Imperial College, London, with Sir Derek Barton and then worked at the Lcole Normale Superieure in Paris. 

The one-step heterocyclic modification of the Julia olefination was discovered by Marc Julia s brother, Sylvestre Julia, who also worked at the Ecole Normale Superieure. The use of tetrazolyl-sulfones was a contribution of Philip Kociehski, and the reaction is sometimes known as the Julia-Kocieilski reaction. 

In view of aU the technical challenges, initially associated with the Wittig reaction, Rhone-Poulenc e.g. opted for the olefination reaction developed by Marc Julia (1922-2010) at the beginning ofthe 1970s (Fig. 7.31). [72]... 

The 1,3-cycloelimination is particularly interesting, because it follows in principle the biosynthetic route. The thermodynamically more stable trans-isomer is favoured. Essential contributions came from work at Rhdne-Poulenc (in collaboration with Marc Julia at the Pasteur Institute) and at Roussel-Uclaf (Jacques... 

The synthesis sequence of a Claisen rearrangement and a 1,3-cycloelimination was developed by Marc Julia, and turned out highly relevant to pyrethroid chemistry. [87] Methallyl alcohol is etherified with the methyl enol ether of methyl laevulinate. After the subsequent Claisen rearrangement, the keto-group is selectively reacted with methylmagnesium iodide. Acid hydrolysis leads to iso-pyrocine, a central building block, which is also accessible by other routes. Con-... 

Beyond the medicinal chemistry sphere, the most striking use of the Smiles rearrangements in synthesis came with the work of Julia and coworkers who transformed the rather tedious two-step olefination developed by his brother, Marc Julia, into an elegant one-step transformation under milder conditions. Further iii5)roved by KociensM and coworkers, this olefination is now recognized as the Julia-Kocienski reaction. An illustrative exaii5)le may be found in the conversion of the tetrazolylsulfone 7 into olefin 8 and tetrazole 9 fScheme 19.41. 

We express our sincere thanks to Dr. Louise G. Edwards who carried out many of the seminal experiments described in this review. Other important contributions were made by Cathleen M. Cradden, Julia C. Lautens, A. Catherine Smith, Christian Sood, and Marc Johnson. 

I am happy to record my indebtedness to Professor Marc Julia, who introduced me to this field of research. I am also grateful to my collaborators, whose names are recorded in this chapter, for their careful experimental work and stimulating discussions. Finally, I wish to thank Professor Nathan Kornblum not only for helping me improve my English but also for his critical discussion. 

The one-port olefination of Sylvestre Julia is operationally simpler and more amenable to scale up than the classical y4-step variant originally reported by Marc Julia. This reaction consists of the replacement of the phenyl sulfone moiety traditionally in the classical reaction, with different heteroaryl sulfones, such as benzothiazol-2-yl (BT, 5) sulfone. This allows the direct olefination process and eliminates the sulfone reduction step. The stereochemistry of the reaction in the synthesis of 1,2-disubstituted alkenes is dependent on the base and solvent. 

Marc Julia and Paris invented this methodology for the preparation of E)-olefin in the synthesis of Liaisons in 1973. The Julia coupling was applied to the synthesis of mono-, di- and tetra-substituted alkenes in the original communication. Kocienski and Lythgoe first demonstrated the trans... 

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