Ferrier I reaction

The name Ferrier (I) reaction, is occasionally used to differentiate this transformation from another reaction, also described by Prof. Ferrier, in which hex-5-enopyranosyl derivatives are transformed into functionalized cyclohexanones, even though this process is also named Ferrier carbocycli-zation, or Ferrier (II) reaction (a) R. J. Ferrier,/. Chem. Soc., Perkin Trans. 1, 1979, 1455 (b) R. J. Ferrier and S. Middleton, Chem. Rev., 1993, 93, 2779. 

One of the most convenient methods for the synthesis of 2,3-unsaturated sugars is the so-called Ferrier-I rearrangement of glycals (O Scheme 6). This reaction allows one to obtain the unsaturated targets via the process in which the double bond migrates from the C1-C2 to the C2-C3 position [1,2,4,5,11],... 

The most important of such processes is the reaction of glycals with alcohols catalyzed with Lewis acids known as Ferrier-I rearrangement [1,2] an example is shown in Figure 10.1. Reaction of glycals with allylsilanes catalyzed by Lewis acids is also a convenient method for the synthesis of C-allyl glycosides (e.g., 3) [2,3],... 

Research in the laboratory of H.M.I. Osborn showed that the use of cyclohexene derivatives as nucleophiles in the Lewis acid-mediated Type I carbon-Ferrier reaction of 3-0-acetylated glycals can be used to prepare unsaturated 3-linked C-disaccharides. The incorporation of the alkene took place with one equivalent of glucal in the presence of boron-trifluoride etherate in 33% yield. The desired C-disaccharide was obtained by selective hydrogenation of the exocyclic double bond in the presence of an endocyclic one. 

D.R. Williams and co-workers accomplished the first total synthesis of marine dolabellane diterpene (+)-4,5-deoxyneodolabelline. The Type I carbon-Ferrier reaction was utilized to assemble the key frans-2,6-disubstituted dihydropyran with complete stereoselectivity (a-anomer). The macrocyclization was carried out with a vanadium-based pinacoi coupiing. 

Laszio, P., Pelyvas, i. F., Sztaricskai, F., Szilagyi, L., Somogyi, A. Novel aspects of the Ferrier carbocyclic ring-transformation reaction. Carbohydr. Res. 1988,175, 227-239. 

The same catalyst has been used by this research group in synthesis of j -amino-aldehydes (146) by combining two catalytic reactions, i.e. a Ni(II) complex-catalyzed isomerization of a double bond and a chiral phosphoric acid (127)-catalyzed aza-Petasis-Ferrier rearrangement in a highly dia-stereo- and enantioselective manner (Scheme 39). ... 

Tri-C -benzyl-D-/nyo-inositol has been achieved from a protected a-D- i /o-hex-5-enopyranoside by way of a Perrier reaction. In a similar way the branched-chain sugar 95 was used as starting material for the synthesis of (-)-laminitol and mytilitol." On the mechanism of the Ferrier reaction, it has been observed that there is loss of stereochemistry at C-6 in the deuterated eno-pyranoside 96 during the formation of the carbocyclic ring." ... 

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. ... 

The aza-Petasis-Ferrier rearrangement is not a true concerted sigmatropic reaction, since it is thought to proceed via C-O bond cleavage of a hemiaminal vinyl ether by the action of an acid catalyst to afford a reactive uninium cation and the enol form of an aldehyde these two intermediates combine subsequently in a Mannich-type process, leading to [i-amino aldehydes (Scheme 40.45) (54). Recently, Terada and Toda used a BlNOL-derived phosphoric acid diester as a catalyst for this interesting reaction [55]. 

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