FERRIER Carbohydrate Rearrangement

This reaction was initiaiiy reported by Perrier in 1979. It is a mercury (II) salt -induced or promoted conversion of 5-enopyranosides into cyclohexanones with stereochemical control, by which substituents at positions 3 and 5 are predominantly in a trans relationship. To differentiate from another reaction also discovered by Perrier (called the Perrier Reaction), this reaction is known as the Ferrier-II rearrangement, " Ferrier-II carbocyclization, Perrier carbocyclization, or Ferrier-II reaction. Occasionally, it is also referred to as the Perrier Reaction. Therefore, it is called the Ferrier-II rearrangement in this book. It is useful in the conversion of carbohydrates into carbosugars, myo-inositols, and other natural products. ... 

In the context of carbohydrate synthesis, a key feature of this effort included a novel and efficient synthesis of axial glycal derivatives utilizing a Ferrier-type rearrangement [17] followed by a [2,3]-sigmatropic rearrangement [18, 19]. The allosamidin effort also spurred development of the method of sulfonamidoglycosylation [20] for the construction of P-linked 2-aminohexoses. Following the invention and... 

P. Tiwari, G. Agnihotriand, and A. K. Misra, Synthesis of 2, 3-unsaturated C-glycosides by HC104-Si02 catalyzed Ferrier rearrangement of glycals, Carbohydr. Res., 340 (2005) 749-752. 

AUylic systems are interesting substrates for the investigation of new methods of C-C bond formation. Some of these methods have been adapted to the carbohydrate field. Enopyrano-sides are often crystalline compounds readily available, for example, using Ferrier rearrangement of tri-0-acetyl glycals with alcohols or its variants with carbon nucleophiles. 

R. J. Ferrier and N. Vethaviyasar, Unsaturated carbohydrates. Part XVII. Synthesis of branched-chain sugar derivatives by application of the Claisen rearrangement, J. Chem. Soc. Perkin Trans, p. 1791 (1973). 

N. Chida, M. Ohtsuka, K. Ogura, and S. Ogawa, Synthesis of optically active cyclohexenones from carbohydrates by catalytic Ferrier rearrangement, Bull. Chem Soc. Jpn. 64 2118 (1991). 

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. 

The addition reaction is used in carbohydrate chemistry as well, resulting in the important Ferrier rearranged fluorides (equation 5)16. In combination with other electrophiles such as sulfur17 and selenium18 it forms the corresponding adducts in good yields (equations 6 and 7). 

Ciment, D M, Ferrier, R J, Unsaturated carbohydrates. Part IV. Allylic rearrangement reactions of 3, 4,6-tri-O-acetyl-D-galactal, J. Chem. Soc. C, 441-445, 1966. 

N. Chida, M. Ohtsuka, K. Ogura, and S. Ogawa, Synthesis of optically active cyclohexenones from carbohydrates by catalytic Ferrier rearrangement, Bull. Chem. Soc. Jpn. 64 2118 (1991). A. S. Machado, A. Olesker, and G. Lukacs, Syntheses of two enantiomeric tetrasubstituted cyclohenanones from 6-deoxyhex-5-enopyranoside derivatives, Carbohydr. Res. 735 231 (1985). 

General reviews on cyclic acetals of carbohydrates have appeared. The cyclic acetals of the aldoses and aldosides have been treated in this Series by de Beider, but inclusion of cyclic acetals of ketoses was beyond the scope of his Chapter. Other articles, by Barker and Bourne, Mills, and Ferrier and Overend, have been concerned with the stereochemistry and conformation of cyclic acetals of the carbohydrate group. The purpose of the present article is to supplement de Beider s Chapter with a description of the pertinent original work, optimal laboratory preparations, properties, and applications of the cyclic acetals of ketoses, and to provide a summary of the known theoretical aspects of their formation, rearrangement, and hydrolysis. 

The Ferrier carbocyclization reaction is a reliable transformation of 5-enopyranosides into carbocycles. As shown in Scheme 12.12 (the carbon numberings in substrates and products have been changed the numbering of substrates is based on the nomenclature of carbohydrates, and the numbering of products is that of cyclohexanones), irrespective of the kinds of substituents and patterns of stereochemistry in the substrates, the rearranged products (15 and 42-46) were obtained in moderate to good yields with relatively high diastereoselectivity. An exception is a reaction of a 4-deoxy-5-enopyranoside derivative, which resulted in a low yield of product 47. 

Mild reaction conditions using catalytic triflates of rare earth metals were also developed. This was based on the better Lewis acid properties of the catalysts, their ready availability and easy handling. An alternative is the use iron(iii) triflate. In carbohydrate chemistry, iron(iii) triflate has only been used for oxidative C-C bond cleavage, thioglycosylation of peracetylated glycosides and type I Ferrier rearrangement of glucal. ... 

For further examples of the Ferrier rearrangement as applied at the start of a synthesis of a thromboxane 62 precursor or of highly oxygenated m-decalinic structures derived from carbohydrates, see Chapter 24. The same reaction applied to the preparation of carbohydrate-based liquid crystals derived from a boronate ester is mentioned in Chapter 17. 

The transformation of glycals (1,2-unsaturated cyclic carbohydrate derivatives) into 2,3-unsaturated glycosyl derivatives, currently termed Ferrier rearrangement, is a well-established synthetic procedure with ample use in the fields of carbohydrate and organic chemistry. This article highlights the developments in the Ferrier rearrangement published in the literature since the last review, in 2013, to early 2016. 

The ring-opening reaction of functionalized 1,2-cyclopropyl carbohydrates is also known, apart from that of unfiinctionalized derivatives. Yu and Pagenkopf demonstrated the formation of oxepine 51 through Ferrier rearrangement-based ring opening... 

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