Coordination Chemistry Reviews 248 (2004) 2165–2192 Review Carbohydrate derivative ligands in asymmetric catalysis Montserrat Diéguez b , Oscar Pàmies b , Aurora Ruiz b , Yolanda D´ ıaz b , Sergio Castillón b , Carmen Claver a,∗ a Departament de Qu´ ımica F´ ısica i Inorgànica, Universitat Rovira i Virgili, Plaça Imperial Tàrraco 1, E-43005 Tarragona, Spain b Departament de Qu´ ımica Anal´ ıtica i Qu´ ımica Orgànica, Universitat Rovira i Virgili, Plaça Imperial Tàrraco 1, E-43005 Tarragona, Spain Received 24 November 2003; accepted 30 April 2004 Available online 6 August 2004 Contents Abstract ............................................................................................................................... 2166 1. Introduction ....................................................................................................................... 2166 2. Carbohydrate ligand types in asymmetric catalysis ..................................................................................... 2166 2.1. Carbohydrate bidentate phosphorus ligands ..................................................................................... 2167 2.1.1. Diphosphines ......................................................................................................... 2168 2.1.2. Diphosphinites ....................................................................................................... 2170 2.1.3. Diphosphites ......................................................................................................... 2173 2.1.4. Mixed P–P ′ ligands ................................................................................................... 2174 2.2. Carbohydrate monodentate phosphorus ligands .................................................................................. 2176 2.2.1. Monodentate phosphines .............................................................................................. 2176 2.2.2. Monodentate phospholes .............................................................................................. 2177 2.2.3. Monodentate phosphinites ............................................................................................. 2177 2.2.4. Monodentate phosphonites ............................................................................................. 2178 2.2.5. Monodentate phosphites ............................................................................................... 2179 2.2.6. Monodentate phosphoroamidites ....................................................................................... 2180 2.3. Carbohydrate P,E-bidentate ligands (E = N, S) .................................................................................. 2181 2.3.1. P,N-ligands .......................................................................................................... 2181 2.3.2. P,S-ligands ........................................................................................................... 2183 2.4. Carbohydrate S,E-ligands (E = N, O, S) ........................................................................................ 2184 2.4.1. S,N-ligands .......................................................................................................... 2184 2.4.2. S,O-ligands .......................................................................................................... 2184 2.4.3. S,S-ligands ........................................................................................................... 2184 2.5. Carbohydrate N and N–N ligands .............................................................................................. 2185 2.6. Carbohydrate O,E-ligands (E = N, O) .......................................................................................... 2187 2.6.1. N,O-ligands .......................................................................................................... 2187 2.6.2. O and O,O-ligands .................................................................................................... 2187 3. Concluding remarks ................................................................................................................ 2189 References ............................................................................................................................ 2190 Abbreviations: BINAP, 2,2-bis(diphenylphosphino)-1,1 ′ -binaphthyl; BSA, N,O-bis(trimethylsilyl)acetamide; COD, 1,5-cyclooctadiene; DEGUPHOS, 1- benzyl-3,4-bis(phenylsulphanyl)pyrrolidine; DIOP, trans-4,5-bis[(diphenylphosphonayl)methyl]-2,2-dimethyl-1,3-dioxolane; DIPAMP, 1,2-ethanediyl-bis(2- methoxyphenyl-phenyl)phosphine; DUPHOS, 1,2-bis((2,5-dimethylphospholano)benzene; ee , enantiomeric excess; MOM, methoxy-ethoxy-methylene; NBD, 2,5-norbornadiene; TADDOL, ,, ′ , ′ -tetraphenyl-2,2 ′ -dimethyl-1,3-dioxolane-4,5-dimethanol ∗ Corresponding author. Tel.: +34 977559574; fax: +34 077559563. E-mail address: claver@quimica.urv.es (C. Claver). 0010-8545/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.ccr.2004.04.009