Recent Developments in the Ferrier Rearrangement

Abstract

Glycals (1,2‐unsaturated, cyclic carbohydrate derivatives) readily undergo (catalyzed) substitution reactions at C‐1 accompanied by allylic rearrangement. This reaction, currently named Ferrier rearrangement, or the Ferrier I reaction, has established itself as a useful synthetic tool for carbohydrate transformations. By means of this reaction, glycals can be converted into highly useful 2,3‐unsaturated glycosides. This review summarizes recent developments in the use of promoters for the Ferrier rearrangement of O‐, N‐, C‐ and S‐nucleophiles with glycals.

Ferrier–Nicholas pyranosidic cations: application to diversity-oriented synthesis

“…Glycals, i.e., Δ 1,2 -unsaturated carbohydrate derivatives, have already shown its usefulness in DOS. For instance, Schreiber and co-workers reported the combination of Ferrier [27,28] and Pauson-Khand [29,30] reactions to gain access to a library of tricyclic compounds [31], whereas Porco and co-workers employed a glycal-derived scaffold to produce a collection of highly substituted tetrahydrofurans [32]. In line with our previous approach to appendage diversity based in polyfunctionalized carbohydrate derivatives, we have studied the behavior of, previously unknown, Ferrier-Nicholas cations, e.g., 4 [33].…”

Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues

“…Initially,w ea ttempted direct arylation of pyranuloses 1a and 1b by aF errier-typer eaction [12] (e.g.,v ia cyclic oxonium ion 2a)o rT suji-Trost-type allyl-aryl coupling [13] (e.g.,v ia allylpalladium 2b) [14] (Scheme 1a). After extensive examination of the variousL ewis acids and palladiump recatalysts alongw ith differenta rylmetaln ucleophiles( see the Supporting Information for the screening conditions), we were disappointed to find that only PhB(OH) 2 /BF 3 ·Et 2 Oo rT iCl 4 /ArZnCl promoted the reactiona nd only gave 7-11% yield of 3.W es peculated that the unsuccessful arylation might be attributed to facile formation of the reactive oxidopyrylium ion 2c throughl oss of water or acetic acid.…”

Tris(Pentafluorophenyl)Borane‐Driven Stereoselective O‐Glycosylation with Glycal Donors under Mild Condition

“…[2] In this context, glycals play an important role in the preparation of various oligosaccharides, glycoconjugates and natural products. [5] Moreover, this chemistry provides a path to achieve versatile chiral intermediates that are useful in the preparation of a variety of bioactive compounds. [5] Moreover, this chemistry provides a path to achieve versatile chiral intermediates that are useful in the preparation of a variety of bioactive compounds.…”

“…[3] Among the different reactions of glycals, Ferrier rearrangement [4] (i. e. the transformation of glycals into 2,3unsaturated glycosyl derivatives) received considerable attention in carbohydrate synthesis. [4][5][6] On the other hand, 2-deoxy-O-glycoside units are found in a wide range of bioactive carbohydrate molecules and natural products (Figure 1). [4][5][6] On the other hand, 2-deoxy-O-glycoside units are found in a wide range of bioactive carbohydrate molecules and natural products (Figure 1).…”

“…[5,8,9] On the other hand, only a limited reports are available for achieving 2-deoxy-O-glycosides directly from glycals with high stereoselectivity. and protic catalysts such as H 3 PO 4 , TFA, HClO 4 · SiO 2 , H 2 SO 4 · SiO 2 etc.…”