Ferrier glycosylation

Glycals can be transformed into 1,6-anhydro sugar derivatives by intramolecular cyclization in the presence of Lewis and Brpnsted acids, a reaction that has been termed the intramolecular Ferrier glycosylation.168 Sharma el al.169 showed that a montmorillonite clay-supported silver reagent can be an efficient catalyst for this transformation. The 1,6-anhydro-2,3-dehydro sugars obtained were then selectively dihydroxylated to furnish 1,6-anhydro saccharides. 

K. Ikeda, Y. Ueno, S. Kitani, R. Nishino, and M. Sato, Ferrier glycosylation reaction catalyzed by Bi(OTf)3-Montmorillonite K-10 Efficient synthesis of 3,4-unsaturated sialic acid derivatives, Synlett (2008) 1027-1030. 

By Ferrier glycosylation of di-O-acetyl-L-rhamnal (28) with the epoxide derivative 117 the disaccharide 118 is obtained. This is trans-opened by lithium iodide according to Fiirst-Plattner s rule. Upon different ways, two interesting products are obtained, either the original C-B disaccharide of aclacinomycin A 120 or its C-5 epimer 119 which contains one sugar in the D-configuration [69]. 

Masson, C, Soto, J, Bessodes, M, Ferric chloride a new and very efficient catalyst for the Ferrier glycosylation reaction, Synlett, 1281-1282, 2000. 

Takhi, M, Abdel-Rahman, A A H, Schmidt, R R, Highly stereoselective synthesis of pseudoglycals via Yb(OTf)3 catalyzed Ferrier glycosylation, Synlett, 427-429, 2001. 

Abada, P. B., Shull, B. K., Koreeda, M. On the mechanism of the iodine-catalyzed ferrier glycosylation reaction. Book of Abstracts, 213th ACS National Meeting, San Francisco, April 13-171997, CARB-091. 

Bi(N03)3 5H20 was described as the optimal catalyst, with respect to other metal nitrates, in the Ferrier glycosylation of alcohols furnishing excellent yields of 0-glucosides with good anomeric selectivity in acetonitrile. Its catalytic ability was found to enhance drastically in the ionic liquid [bmimjfPF j [35]. 

Scheme 18 Lewis-acid triflates as catalysts in the Ferrier glycosylation of 41.

Thioglycosides were the first example of an anomeric derivatization that serves the dual role of protection and activation. They were introduced in glycosylation reactions by Ferrier et al. in 1973, who used mercury(II) salts as activator.1 After the development of improved methods of their synthesis and activation, thioglycosides together with trichloroacetimidates are now the most commonly used glycosyl... 

Thioglycosides were first introduced in glycosidation reactions by Ferrier in 1973 [31], who used the ethylthio group at the anomeric position. Subsequently, Hanessian [32] demonstrated the usefulness of the 2-pyridylthiol. Currently, the phenylthio and the ethylthio carbohydrate derivatives are the most commonly used glycosyl donors from this class of... 

V. Ferrieres, J.-N. Bertho, and D. Plusquellec, A new synthesis of 0-glycosides from totally O-unprotected glycosyl donors, Tetrahedron Lett. 36 2749 (1995). 

Starting from 1,5-anhydro-2,3,4-tri-0-benzoyl-6-deoxy-D-ura >/ o-hex-1 -enitol (48), an unusual approach to the synthesis of disaccharides of serogroup A and D has applied the allylic rearrangement glycosylation procedure of Ferrier [127] to obtain an a-D-< rj//zTO-hex-2-enopyranosyl residue in the disaccharide 49a. Reduction of the 2-enopyranose double bond gave both the paratose (ribo) 49b and tyvelose (arabino) 49c products [28]. 

The Ferrier reaction of glycal derivatives has been extensively studied and recently reviewed <2001TCC153>. Additionally, the transformation of glycals into 2,3-unsaturated glycosyl derivatives has also been reviewed... 

Chervin, S M, Abada, P, Koreeda, M, Convenient, in situ generation of anhydrous hydrogen iodide for the preparation of a-glycosyl iodides and vicinal iodohydrins and for the catalysis of Ferrier... 

Koreeda, M, Houston, T A, ShuU, B K, Klemke, E, Tuinman, R J, Iodine-catalyzed Ferrier reaction. 1. A mild and highly versatile glycosylation of hydroxyl and phenolic groups, Synlett, 90-92, 1995. 

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