Asymmetric synthesis of tertiary thiols and thioethers
- Jonathan Clayden and
- Paul MacLellan
Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68
Graphical Abstract
Figure 1: Seven out of the ten top selling drugs in the USA in 2009 contain sulfur. Figures in italics are to...
Figure 2: Naturally occurring organosulfur compounds glutathione and (R)-thioterpineol.
Figure 3: Methods for the synthesis of chiral tertiary thiol 1.
Scheme 1: Preparation of thioethers 4 from α-hydroxy esters.
Scheme 2: Nucleophilic substitution in α-aryl-α-hydroxy esters.
Scheme 3: Preparation of α,α-dialkylthioethers.
Scheme 4: Preparation of α-cyanothioacetate 12.
Scheme 5: Synthesis of (R)-(+)-spirobrassinin.
Scheme 6: Opening of cyclic sulfamidates with thiol nucleophiles.
Scheme 7: Synthesis of androgen 20.
Scheme 8: Synthesis of (+)-BE-52440A.
Scheme 9: The Mitsunobu reaction.
Scheme 10: Mitsunobu substitution at a quaternary centre.
Figure 4: Initially assigned structure of hexacyclinol.
Scheme 11: Preparation of thioether 29.
Scheme 12: Thioethers 33 prepared from phosphinites 31.
Scheme 13: Preparation of enantiomerically pure thiol 39.
Scheme 14: Thioethers prepared by a modified Mitsunobu reaction.
Scheme 15: Nucleophilic conjugate addition.
Scheme 16: Asymmetric addition to cyclic enones.
Scheme 17: Preparation of thioether 45.
Scheme 18: Catalytic kinetic resolution of the enantiomers of enone 46.
Scheme 19: Organocatalytic conjugate addition to nitroalkenes 49.
Scheme 20: Preparation of β-amino acid 54.
Scheme 21: Sulfur migration within oxazolidine-2-thiones 56.
Scheme 22: Preparation of thiols 62 by self-regeneration of stereocentres.
Scheme 23: Synthesis of (5R)-thiolactomycin.
Scheme 24: Preparation of tertiary thiols and thioethers via α-thioorganolithiums.
Scheme 25: Diastereoselective methylation of organolithium 71.
Scheme 26: Addition to lithiated thiocarbamate 75.
Scheme 27: Configurational lability in unhindered α-lithiothiocarbamates.
Scheme 28: Configurational stability in bulky α-lithiothiocarbamates.
Scheme 29: Asymmetric functionalisation of secondary benzylic thiocarbamates.
Scheme 30: Methylation of lithioallyl thiocarbamates.
Scheme 31: Asymmetric preparation of tertiary allylic thiols.
Scheme 32: Asymmetric preparation of thiols 96 by aryl migration in lithiated thiocarbamates.
