Ferrier reaction

Ferrier Reaction of Tri-O-acetyl-D-glucal with Different Nucleophiles in the Presence of HC104-Si02 Reagent82... 

G. V. M. Sharma, K. C. V. Ramanaiah, and K. Krishnudu, Clay montmorillonite in carbohydrates use of claysil as an efficient heterogenous catalyst for the intramolecular Ferrier reactions leading to 1,6-anhydro rare saccharides, Tetrahedron Asymm., 5 (1994) 1905-1908. 

Acetylglycosyl aryl ethers, obtained by the Ferrier reaction of acetylglycals with phenols, can be de-acetylated and converted into the benzyl ethers in a one-pot reaction in the presence of a quaternary ammonium salt (see, e.g. Scheme 3.3) [30]. 

As the precursor for the B unit, the selectively benzylated -fucal derivative 75- could be obtained crystalline from L-fucal by applying a phase-transfer-catalyzed process T64). By a Ferrier reaction of di-O-acetyl-L-rhamnal and a subsequent retro enol ether formation trough hydride attack at C-3 (71.) the -amicetal 72 was obtained (64) this reaction was concurrently also es-cribed by others (72). 

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. 

By use of the Ferrier reaction with boron trifluoride catalysis, the formation of both the epimeric a-linked hex-2-enopyranosides 105 [64] and 106 [65] is achieved. 

The drawback of this method arises from the rearrangement of glycals, under the acidic conditions of the reaction, to the 2,3-unsaturated enoses (Ferrier reaction). The other problem is the incompatibility of some acid-labile protective groups with the relatively strong reaction conditions. These difficulties led to the development of different methodologies with the aim of minimizing the... 

T. Noshita, T. Sugiyama, Y. Kitazumi, and T. Oritani, Reinvestigation of phenolic Ferrier reaction selective sysnthesis of aryl 0-A2-glycosides, Biosci., Biotechnol., Biochem., 59 (1995) 2052-2055. 

H. B. Mereyala, K. C. Venkataramanaiah, and V. S. Dalvoy, Synthesis of 1,6-anhydro-2,3-dideoxy-jS-D-eryi/iro- and -t/jreo-hex-2-enopyranose from 3,4-di-O-substituted glycals by a facile intramolecular Ferrier reaction, Carbohydr. Res., 225 (1992) 151-153. 

From the retrosynthetic perspective (Fig. 2), the tetracyclic structure is expected to be accessible by tandem Michael-Dieckmann type reaction of 59 with 60. The suitably substituted chiral intermediate 59 would be synthesized by Diels-Alder reaction of the cyclohexenone 57 and the silyloxybutadiene 58. The regio- and stereoselectivities are established as a consequence of the dienophile geometry according to Gleiter s theory (29). Compound 57 could be obtained from 51 through Ferrier reaction of 54. 

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... 

In the previous subsection, it was shown that the Ferrier reaction offers an opportunity to convert glycal derivatives into unsaturated sugar derivatives, which have an isolated double bond between C(2) and C(3). The Tipson-Cohcn reaction is another important reaction for the introduction of isolated double bonds.29 In this procedure, a cis or tram diols are converted into disulfonates (mesylates or tosylates) which are reductively eliminated with sodium iodide and zinc in refluxing DMF (Scheme 3.6a). In this reaction, the C(3) sulfonate is substituted by an iodide, which then is reductively removed by zinc with concomitant elimination of the second sulfonate moiety, introducing a double bond. Stereoelectronic effects make nucleophilic substitutions at C(3) more favourable than similar reactions at C(2) (see Section 3.2.3). Probably, the elimination proceeds through a boat conformation. In this case, the iodide and tosylate are in a syn relation. In most cases, E2 elimination proceeds via a transition state involving an anti orientation. Nevertheless, syn elimination becomes the dominant mode of reaction when structural features prohibit an anti orientation. 

The Ferrier reaction was used as a key step for the synthesis of 108 from D-glucose (Scheme 14).72 Methyl y-D-glucopyranoside (101) was converted into benzyl ether 103 via the alkene 102.73 74 Regioselective 2,6-ditosylation of 101, followed by methoxymethylation with dimethoxymethane and P2O5, afforded alkene 102, which... 

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. 

Carbasugars Cyclitols Glycosidase inhibitors Cyclophelitol Allosamidin Trehazolin Neuraminidase inhibitor Tamiflu Intramolecular [3+2] cycloaddition The Ferrier reaction... 

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