FERRIER Carbohydrate synthesis

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. 

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). 

Organometallic methods, with the possible exception of those involving the stoichiometric generation of enolates and other stabilized carbanionic species 140], have seldom been used in carbohydrate chemistry for the synthesis of cyclohexane and cyclopentane derivatives. The present discussion will not cover these areas. The earliest of the examples using a catalytic transition metal appears in the work of Trost and Runge [41], who reported the Pd-catalyzed transformation of the mannose-derived intermediate 22 to the functionalized cyclopentane 23 in 98% yield (Scheme 10). Under a different set of conditions, the same substrate gives a cycloheptenone 24. Other related reactions are the catalytic versions of the Ferrier protocol for the conversion of methylene sugars to cyclohexanones (see Chap. 26) [40,42,43]. 

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 synthetic procedures available to the carbohydrate chemist have been largely dominated by standard reactions proceeding by heterolytic processes within a chiral matrix. The preparative utility of radical-mediated reactions has, however, been amply demonstrated in recent years. The chapter contributed here by L. Somsak (Debrecen) and R. J. Ferrier (Wellington), on bromination reactions of carbohydrates proceeding by radical processes integrates the literature related to Ferrier s pioneering work in this area and underscores its excellent potential in synthesis. 

G. S. Bethell and R. J. Ferrier, The relayed introduction of alkylthio-groups into carbohydrates derivatives A novel synthesis of amicetose, J. Chem. Soc. Perkin / (1993) 1400-1405. 

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. 

V. Ferrieres, J.-N. Bertho, and D. Plusquellec, A convenient synthesis of alkyl D-glycofuranosiduronic acids and alkyl D-glycofuranosides from unprotected carbohydrates, Carbohydr. Res., 311 (1998) 25-35. 

Ferrier, R.J. and Rrasad, N. 1969. Unsaturated carbohydrates. Fart IX. Synthesis of 2,3-dideoxy-a-D-eryf/jro-hex-2-enopvranosides from tri-O-acetyl-D-elucal. Journal of Chemical... 

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). 

Ferrier, R. J. Synthesis of enantiomerically pure non-carbohydrate compounds. Carbohydr. Chem. 1995, 27, 312-360. 

R. Ferrier and R. Fumeaux, Synthesis of l, 2-trans-related 1-thioglycoside esters, Carbohydr. 

---