Rearrangement Ferrier glycal allylic

More complex products made directly from the corresponding glycols O OH O 

By spontaneous sigmatropic rearrangement of the glycal 3-trichloroacetimidate made with NaH, CI3CCN, 

Name Reactions, 4th ed., DOI 10.1007/978-3-642-01053-8 96, Springer-Verlag Berlin Heidelberg 2009 

W-iodonium dicollidine perchlorate (65%, mainly a) pent-4-enoyloxy 

Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications, DOI 10.1007/978-3-319-03979-4 103, Springer International Publishing Switzerland 2014 

A variant using inexpensive Montmorillonite K-10 clay as the catalyst  

Toshima, K. Ishizuka, T. Matsuo, G. Nakata, M. Kinoshita, M. J. Chem. Soc., Chem. Commun. 1993, 704-705. 

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Ferrier RJ (2001) Substitution-with-Allylic-Rearrangement Reactions of Glycal Derivatives. 215 153-175... 

The Lewis acid-mediated allylic rearrangement of glycals like 28 to glycosides 29 known as the Ferrier-reaction is well known in carbohydrate chemistry [14-16]. It yields predominantly a-configurated hex-2-enopyranosides (cf. 29), either in the d-or L-sugar series. These may be hydrogenated to glycosides like the 2,3,6-trideoxy-species 30. 

In order to simplify these preparations, Boivin et al. [52] made use of the allylic rearrangement reaction (Ferrier type) which was one of the first accesses to 3-amino glycals. By use of azide as the nucleophile, the L-arabino configurated glycal 78... 

R. J. Ferrier, Substitution-with-allylic rearrangement reactions of glycal derivatives, in A. E. Stutz (Ed.), Topics in Current Chemistry, Vol. 215, Springer-Verlag, Berlin, 2001, pp. 153-175. 

R. Blattner, R. J. Ferrier, and R. H. Furneaux, Intervention of catalytic amounts of water in the allylic rearrangement of glycal derivatives, Tetrahedron Asymmetry, 11 (2000) 379-383. 

Ferrier, R.J. 2001. Substitution with allylic rearrangement reactions of glycal derivatives. 

In general, the Ferrier reaction can be considered as an allylic rearrangement, which implies displacement of the C-3 substituent of a glycal, followed by attack of a given (0-, N-, C- or S-) nucleophile at the anomeric (C-1) position of an intermediate allylic oxycarbenium ion, 2. The latter reacts with nucleophilic species to provide mixtures of adducts (3) in which the pseudoaxial glycosides predominate. 

TABLE 37.4. Ferrier Rearrangement of Glycal Allylic Ethers... 

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