Schlosser Modification

The Schlosser Modification of the Wittig Reaction allows the selective formation of E-alkenes through the use of excess lithium salts during the addition step of the ylide and subsequent deprotonation/protonation steps.

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Mechanism of the Schlosser Modification

Lithium salts effect, that the intermediate betaines (see Wittig Reaction) do not react further. These lithiobetaines which are quite stable may be deprotonated. Deprotonation is equal to the lost of one stereogenic center. Use of a steric hindered proton donator then leads to the trans lithiobetaine. The reaction takes "normal" course, if lithium is exchanged by potassium.

Recent Literature

Convergent and Stereoselective Synthesis of Trisubstituted E-Alkenyl Bromides and Iodides via β-Oxido Phosphonium Ylides
D. M. Hodgson, T. Arif, J. Am. Chem. Soc., 2008, 130, 16500-16501.

β-Lithiooxyphosphonium ylides, generated in situ from aldehydes and Wittig reagents, react readily with halomethyl esters to form trisubstituted Z-allylic esters. The methodology was applied to a total synthesis of a geranylgeraniol-derived diterpene.
D. M. Hodgson, T. Arif, Org. Lett., 2010, 12, 4204-4207.