Carbon-Ferrier rearrangement

Scheme 9.46 Carbon-Ferrier rearrangement with allyl silane as nucleophile.

The carbon-Ferrier rearrangement, in which appropriately functionalized glycols react with a variety of C-nucleophiles at the anomeric carbon with loss of a C(3) substituent, has been reviewed. ... 

The Perrier rearrangement has been reviewed and the carbon-Ferrier rearrangement of functionalized glycals with a variety of carbon nucleophiles including allyltrimethylsilanes, alkynyltrimethylsilanes, and silyl cyanides at the anomeric carbon... 

Addition to Various Electrophiles. Various Lewis acids promote the addition of the reagent to an allylic acetate, following a carbon-Ferrier rearrangement pathway. Tita-nium(IV) chloride promotes the addition of the reagent to 2,2-dialkoxycyclopropanecarboxylic esters to give 3-alkoxy-2-cyclopentenones (eq 13). ... 

AUylic systems are interesting substrates for the investigation of new methods of C-C bond formation. Some of these methods have been adapted to the carbohydrate field. Enopyrano-sides are often crystalline compounds readily available, for example, using Ferrier rearrangement of tri-0-acetyl glycals with alcohols or its variants with carbon nucleophiles. 

Alternatively, Pd(0) adds oxidatively to the double bond of a glycal derivative resulting in the formation of a ir-allyl complex, which may react with carbon nucleophiles to give C-glycosides with a double bond between C(2) and C(3).26 A rt-allyl complex may also be formed starting from a Ferrier rearrangement product (2,3-unsaturated sugar derivative).22... 

The Ferrier carbocyclization reaction is a reliable transformation of 5-enopyranosides into carbocycles. As shown in Scheme 12.12 (the carbon numberings in substrates and products have been changed the numbering of substrates is based on the nomenclature of carbohydrates, and the numbering of products is that of cyclohexanones), irrespective of the kinds of substituents and patterns of stereochemistry in the substrates, the rearranged products (15 and 42-46) were obtained in moderate to good yields with relatively high diastereoselectivity. An exception is a reaction of a 4-deoxy-5-enopyranoside derivative, which resulted in a low yield of product 47. 

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