Glycidyl tosylate

Delgado, A. Leclerc, G. Cinta Lobato, M. Mauleon, D. Tetrahedmn Lett. 1988,29,3671. 

Yamamoto, Y Asao, N. Meguro, M. Tsukada, N. Nemoto, H. Sadayori, N. Wilson, J. G. Nakamura, H. Chem. Commun./J. Chem. Soc., Chem. Commun. 1993, 1201. 

Johnson The Upjohn Company, Kalamazoo, MI, USA Carmen E. Burgos-Lepley Cortech, Denver, CO, USA 

Form Supplied in white solid commercially available. 

Analysis of Reagent Purity enantiomeric purity can be assessed by the following procedures. Procedure A (no deriva-tization) Chiral HPLC on a Diacel OD column (10 pim, 0.46 X 25 cm) flow, 0.7 mL min 99 1 hexane-2-propanol Ir (5) enantiomer, 51.2 min (R) enantiomer, 53.9 nrin. Procedure B the reagent is opened to the iodohydrin the crude iodohydrin is esterified with (R)-(+)-a-methoxy-a-(trifluoromethyl)phenylacetyl (MTPA) chloride the resulting crude MTPA ester is analyzed by chiral HPLC and H NMR.  

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The R enantiomer was prepared the same way from (-)-glycidyl tosylate. References... 

Preparative Methods the title reagent (1) is obtained in 40% overall yield by the zeolite-modified Sharpless asymmetric epoxi-dation of allyl alcohol, using D-(-)-diisopropyl tartrate (DIPT) to obtain (S)-(l) and l-(+)-DIPT to obtain (R)-(l), followed by in situ low-temperature tosylation of glycidol. Alternatively, (R)- and (S)-(l) can be prepared by direct sulfonylation of commercially available chiral Glycidol, Note that the relative configuration of (R)-glycidyl tosylate is the same as that of (5)-glycidol. 

Alkylation Resin 41 (1 g, based on Wang resin, 1.11 mmol g ), lithium iodide (1 equiv.), and glycidyl tosylate (10 equiv.) were suspended in dry NMP (8 mL) and the mixture was stirred for 10 min at ambient temperature under an argon atmosphere. Lithium bis(trimethylsilyl)amide (1 m in THF, 2 equiv.) was then added dropwise and the reaction mixture was stirred overnight. Thereafter, the resin 42 was filtered off and washed with DMF (10 times), DMF/CH2CI2 (1 1, five times), and CH2CI2 (five times), and dried in vacuo. 

The synthesis of phospholipids and analogues, mainly by well-established methods, continues to be actively pursued. A new, stereospecific route to functionalised ether phospholipids, e.g. (54) and (55), as analogues of l-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine (PAF) and modulation phospholipids, has been reported. The route uses (/ )-glycidyl tosylate (56) as the chiral precursor... 

TABLE 1. Regioselectivity in the reaction of (S)-glycidyl tosylate (14) with hydroxyaryl nucleophiles... 

Glycidyl groups can be attached to PPE in a first step by increasing the amount of pendent hydroxyl groups, e.g., by a redistribution reaction. In a second step, these hydroxyl groups are allowed to react with epichlo-rohydrin. " Other reagents that have been claimed to be useful are epibro-mohydrin and glycidyl tosylate. 

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