Carbohydrate-modified carbene complexes can be synthesised by combinin
g a sugar electrophile with a metalate nucleophile or vice versa. Acyc
lic sugar skeletons adopt conformations that are controlled by the min
imisation of 1,3-interactions and are not significantly affected by th
e incorporation of a metal fragment. Thus, the latter can be used excl
usively for reactivity tuning. Sugar carbene complexes undergo regio-
and stereoselective ligand-and metal-centred reactions such as C-2-hom
ologisation and benzannulation.