Ferrier-type rearrangement

This methodology has been used for the synthesis of the C3-C14 segment 24 of the antitumor agent laulimalide 23 (Scheme 4.22) [35]. The constrained chiral BOX ligand 21c in combination with Cu(OTf)2 afforded dihydropyrane 6f by a cycloaddition reaction in good yield and ee this was converted to the C3-C14 segment 24 via a Ferrier-type rearrangement in several steps. 

Ferrier-type rearrangement to give glycal 74 [25] (Scheme 18). Spiroketals 75 are then obtained after desilylation. A similar sequence of reactions based on cyclic sulfate 76 furnishes adduct 77 which, after desilylation to give 78, provides spiroketals 79 upon N-iodosuccinimide (NIS) treatment. 

Choudhury et al." employed an unprecedented palladium mediated Ferrier type rearrangement glycosidation and succeeded in synthesis of 226 (Scheme 12.53). It is noteworthy that classical Ferrier rearrangement does not work on furanoid glycals. 

Ferrier-type rearrangement,or Perrier reaction, but is called the Perrier reaction in this book to differentiate it from another type of rearrangement also developed by Perrier and co-workers. 

A chiral phosphoric acid-catalyzed Petasis-Ferrier-type rearrangement of a seven-membered cyclic vinyl acetal resulted in the formation of a chiral tetrahydrofuran species. It was found that nonclassical hydrogen bonds between the catalyst and the substrate play an important role in controlling the stereoselectivity (14CS3515). 

Scheme 3.5 Stereoselective Petasis-Ferrier-type rearrangement catalyzed by chiral phosphoric acids. (Data from Kanomata, K. et al, Chem. Sci, 5,3515-3523,2014.)...

Kanomata, K. Toda, Y. Shibata, Y. Yamanaka, M. Tsuzuki, S. Gridnev, I. D. Terada, M. Secondary Stereocontrolling Interactions in Chiral Bronsted Acid Catalysis Study of a Petasis-Ferrier-Type Rearrangement Catalyzed by Chiral Phosphoric Acids. Chem. Sci. 2014,5,3515-3523. 

Only very recently [77], Sinay et al. presented a series of Ferrier-type rearrangements [78] of 5,6-unsaturated sugars to cyclohexenones. In this study, the same catalyst, applied to the reaction of furanyl C-glycoside 216, yielded exclusively, after reduction of the intermediate ketone, cyclohexanol 217 (Scheme 45). A conceivable Claisen rearrangement to a bicyclic product 218 was apparently not observed. 

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... 

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