Diol synthesis

Alkylations of 4-cyano-l,3-dioxanes (cyanohydrin acetonides) represent a highly practical approach to syn-l,3-diol synthesis. Herein we present a comprehensive summary of cyanohydrin acetonide chemistry, with particular emphasis on practical aspects of couplings, as well as their utility in natural product synthesis. Both 4-acetoxy-l,3-dioxanes and 4-lithio-1,3-dioxanes have emerged as interesting anri-l,3-diol synthons. The preparation and utility of these two synthons are described. 

The Oxygenation of Vinyl Cyclopropanes as an Entry Into Stereoselective 1,3-Diol Synthesis," Feldman. K.S. SvnletL 1995, 217... 

The general procedure for the diol synthesis is as follows. A solution of 11,88mmol olefin. 

Asymmetric diols synthesis from olefins over the hybrid catalyst of TI-MCM4I and Co(lll) Salen complexes. 

H. Nishiyama, T. Kitajima, M. Matsumoto, and K. Itoh, Silylmethyl radical cyclization New stereoselective method for 1,3-diol synthesis from allylic alcohols, J. Org. Chem. 49 2298 (1984). 

OXAZOLIDINECARBOXYLATE has previously been described in Volume 70 of Organic Sytheses. An alternative procedure for the preparation of this compound is presented in this volume along with its use in a dia-stereoselective addition reaction with 2-TRIMETHYLSILYLTH1AZOLE to provide a compound bearing a 2-amino-1,3-diol substructure that appears in a variety of natural products. The conversion of abundantly available isosorbide into OSO ISOPROPYLIDENE-l ti-DIANHYDRO-d-GLUCITOL provides a potentially useful carbohydrate-deri ved material for the use in complex tetrahydrofuran synthesis. Finally, asymmetric reduction of an a,j9-unsaturated acylstannane with (R)-BINAL provides access to (S,E)-l-(METHOXYMETHOXY)-l-TRIBUTYLSTANNYL-2-BUTENE, an a-alkoxy allylstannane that has been used in enantioselective vicinal diol synthesis amongst other transformations. 

Feldman, K.S. 1995. The oxygenation of vinylcyclopropanes as an entry into stereoselective 1,3-diol synthesis. Synlett, 3 217-25. 

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