Oxidation Grieco method

If the 4-hydroxy group is free, then when using methanol as solvent, anomeric lactol ethers 356 are formed with high yields (equation 95). Oxidation by the Grieco method leads to y-substituted y-lactones 357 (equation 95)209,224,231,243,249,260 ... 

Grieco has applied the use of the unusual solvent system LiC104-Et20 to effect a Bronsted acid-catalyzed electrophilic substitution of indole by jS,jS-disubstituted allylic alcohols en route to YCK as shown in Scheme 5 (59). The synthesis commenced with the diol 89 (available in two steps from isophorone 84), which on treatment with indole in LiC104-Et20 containing 0.01 equivalent of acetic add furnished the substitution product 90 in 86% yield. In the face of the failure of standard methods, oxidation to the aldehyde required conversion to the alkoxymagnesium bromide, followed by treatment... 

Methods for the Synthesis of a-Methylene Lactones P. A. Grieco, Synthesis, 1975, 67-82. Ruthenium Tetroxide Oxidations J. L. Courtney and K. F. Swansborough, Rev. Pure Appl. Chem., 1972, 22, 47-54. 

Hydrolysis of vinyl sulfides to carbonyl compounds. Corey and Shulman (3, 97) in 1970 fhst reported that vinyl sulfides could be hydrolyzed to ketones with mercuric chloride in aqueous acetonitrile. This method, sometimes in combination with mercuric oxide or calcium carbonate (4, 38, 39), has been widely used. However, recently, Grieco, Cohen, and collaborators have reported that mercuric chloride hydrolysis of vinyl sulfides of type (1) to aldehydes is not generally successful. They have found a very simple solution illustrated for hydrolysis of (2) to n-heptanal (4). 

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