Reagent for organic syntheses

L.F. Fieser and M. Fieser, "Reagents for Organic Synthesis" (Vol. I, p, 911) John Wiley and Sons, New York, London, Sydney (1967). 

L.F. Fieser, Reagents for Organic Synthesis, Vol 1, Wiley, N.Y., 1967 or standard textbooks. 

Before describing how p keto esters are used as reagents for organic synthesis we need to see how these compounds themselves are prepared The mam method for the prepa ration of p keto esters is the Claisen condensation... 

Other Heterocyclic Compounds. l,3-DichlorotetrahydroquiQa2oliQe-2,4-dione [23767-45-5] is useful as a laundry bleach. 2-Chloro-4-thia2olines are useful reagents for organic synthesis (167). N-Chloropiperidines, A/-chloropiperidones, and... 

W. P. Weber, Silicon Reagents for Organic Synthesis, Springer-Verlag, New York, 1983, pp. 255-272. 

Chemical tests for particular types of impurities, e.g. for peroxides in aliphatic ethers (with acidified KI), or for water in solvents (quantitatively by the Karl Fischer method, see Fieser and Fieser, Reagents for Organic Synthesis J. Wiley Sons, NY, Vol 1 pp. 353, 528, 1967, Library of Congress Catalog Card No 66-27894). 

L.A. Paquette (Ed.). The Encyclopedia of Reagents for Organic Synthesis, 8 Volume set, J Wiley Sons, New York, 1995. ISBN 0471936235. 

A.J. Pearson and W.R. Rouse, Handbook of Reagents for Organic Synthesis, 4 Vol. Set, J. Wiley Sons, Chichester, 2001. ISBN 04719878911. 

A. W P. Jarvie, Organomet Chem. Rev., Sect A 6 153 (1970) W. P. Webei Silicon Reagents for Organic Synthesis, Springer-Verlag, Berlin, 1983 E. W Colvin, Silicon in Organic Synthesis, Butterworths, London, 1981. 

A detailed procedure for the use of MCPBA recently appeared in Reagents for Organic Synthesis by Fieser and Fieser. The commercially available MCPBA (Aldrich) is 85% pure the contaminant, m-chlorobenzoic acid, can be removed by washing with a phosphate buffer of pH 7.5. The epoxidation is usually performed as follows a solution of 3 -acetoxy-5a-androst-16-ene (2.06 g, 6.53 mmoles) in 25 ml of chloroform (or methylene dichloride) is chilled to 0° in a flask fitted with a condenser and drierite tube and treated with a solution of commercial MCPBA (1.74 g, 20% excess) in 25 ml chloroform precooled to the same temperature. The mixture is stirred and allowed to warm to room temperature. After 23 hr (or until TLC shows reaction is complete) the solution is diluted with 100 ml chloroform and washed in sequence with 100 ml of 10% sodium sulfite or sodium iodide followed by sodium thiosulfate, 200 ml of 1 M sodium bicarbonate and 200 ml water. The chloroform extract is dried (MgS04) and evaporated in vacuo to a volume of ca. 10 ml. Addition of methanol (10 ml) followed by cooling of the mixture to —10° yields 0.8 gof 16a,17a-epoxide mp 109.5-110°. Additional product can be obtained by concentration of the mother liquor (total yield 80-90%). 

Perbenzoic acid and monoperphthalic acid are used in the same manner as MCPBA but a fresh solution of these reagents is usually required syntheses for these reagents can also be found in Fieser and Fieser s Reagents for Organic Synthesis. A microtechnique for perbenzoic acid epoxidation has also been described. ... 

N-Methylmorpholine Oxide-Hydrogen Peroxide Oxidation. The preparation of A-methylmorpholine oxide-hydrogen peroxide is described in Reagents for Organic Synthesis by L. Fieser and M. Fieser. 

A large variety of salts of triflic acid formed both from metals and nonmetals are known Many of these salts are versatile reagents for organic synthesis because of such properties of the tnflate anion as very low nucleophilicity and low coordinating ability However, despite low nucleophilicity, the triflate anion can combine with carbocationic intermediates under appropriate conditions to form triflate esters [116, 117, II8. ... 

Of more immediate use for the organic chemist is the remarkable compilation by L. F. Fieser and M. Fieser, Reagents for Organic Synthesis, Wiley/Interscience. As of this writing. Volume 1 (1967) and Volume 2 (1969) have appeared, and future volumes are anticipated. In their usual thoroughgoing style, the Fiesers have listed hundreds of organic reagents, brief discussions of their sources and applications, and many literature references. 

M. Pieser, L. Pieser, Reagents for Organic Synthesis, Vol. 1, Wiley-Inter-science. New York, 1967, 936, and references therein. 

The tartrate ester modified allylboronates, the diisopropyl 2-allyl-l,3,2-dioxaborolane-4,5-di-carboxylates, are attractive reagents for organic synthesis owing to their ease of preparation and stability to storage71. In the best cases these reagents are about as enantioselective as the allyl(diisopinocampheyl)boranes (82-88% ee with unhindered aliphatic aldehydes), but with hindered aliphatic, aromatic, a,/l-unsaturated and many a- and /5-alkoxy-substituted aldehydes the enantioselectivity falls to 55-75% ee71a-b... 

Methylalumoxane as a highly Lewis-acidic reagent for organic synthesis [107]... 

---