Anions Anomeric effect

While the lone pair on the hydroxyl oxygen of hydroxamic acid 77 would be tightly bound resulting in a weak noH-cr N Qr interaction, the anion 78 would possess a high energy pair of electrons that would enhance the anomeric effect and drive the rearrangement. 

The influence of the classical anomeric effect and quasi-anomeric effect on the reactivity of various radicals has been probed. The isomer distribution for the deu-teriation of radical (48) was found to be selective whereas allylation was non-selective (Scheme 37). The results were explained by invoking a later transition state in the allylation, thus increasing the significance of thermodynamic control in the later reactions. Radical addition to a range of o -(arylsulfonyl)enones has been reported to give unexpected Pummerer rearrangement products (49) (Scheme 38).A mechanism has been postulated proceeding via the boron enolate followed by elimination of EtaBO anion. 

Alkyl halides, hydroperoxide synthesis, 327-8 Alkyl hydroperoxides anion ligands, 114-19 covalent radii, 114, 118-19 dihedral angles, 119 geometric parameters, 115-8 tetrahedral distortion, 119 artemisinin formation, 133-4 chlorotriorganosilane reactions, 779-83 crystal structure, 105-14 anomeric effect, 110-11 geometric parameters, 106-9 hydrogen bonding, 103-5, 111-14 tetrahedral distortion, 110 determination, 674... 

Glycosyl acetates react with tributyltin methoxide to give glycosyl tributylstannyl ethers. As with glycosyl anions,337"339 the anomeric effect causes... 

C-Glycosylation Oxocarbenium cation Anomeric radical Anomeric anion Stereoelectronic effect... 

Stereochemical control in 0-alkylative /3-glycosylation relies on the kinetic anomeric effect [110] namely, that the oxyanion derived from a reducing sugar is more reactive in its 8-ori-ented form 71B than the corresponding a-anion 71A which should be more abundant. This tactic has met with partial success in cases of reactive substrate [111] (O Scheme 38). For example, reaction of 72 with a primary triflate in THF in the presence of NaH afforded the 8-glycoside in 62% yield. 

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