1. Introduction.- 2. Synthesis of 3-Amino-2,3,6-Trideoxyhexoses from Carbohydrates.- 2.1 Synthesis of 2-deoxyhexose derivatives.- 2.1.1 Preparation of 2-deoxyhexopyranosides from glycals and glycal esters.- 2.1.2 Synthesis of 2-deoxyhexose analogs from oxirane and sulfonate ester derivatives.- 2.1.3 Synthesis of 2-deoxyhexose derivatives by means of the chain-elongation of pentoses.- 2.1.4 Cleavage of the 2-phenyl-l,3-dioxolane-type acetal function of hexose derivatives.- 2.1.5 Miscellaneous methods.- 2.2 Introduction of the C-3 amino function into mono- and dideoxyhexose derivatives.- 2.2.1 Displacement reactions of sulfonate esters and halogeno derivatives with nitrogen nucleophiles.- 2.2.2 Ring opening of anhydro- and epiminohexopyranosides with nitrogen nucleophiles.- 2.2.3 Reduction of 3-oximino-2,3-dideoxyhexopyranosides.- 2.2.4 Synthesis and transformation of 3-deoxy-3-nitrohexopyranosides into 3-amino-3-deoxyhexose derivatives.- 2.2.5 Preparation of 3-amino-3-deoxyhexoses from hex-2-enopyranoside (pseudoglycal) derivatives.- 2.2.6 Synthesis of 3-amino-3-deoxyhexose derivatives by means of the allylic azide rearrangement reaction.- 2.2.7 Miscellaneous methods.- 2.3 Simultaneous generation of the C-3 amino and C-2 deoxy functions.- 2.4 2-Halogeno analogs of 3-amino-3-deoxy-hexopyranosides.- 2.4.1 Syntheses via 2,3-epiminohexopyranoside intermediates.- 2.4.2 Syntheses from 2-hydroxy- and 2-O-sulfonyl derivatives.- 2.4.3 Simultaneous introduction of the 3-amino- and 2-halogeno substituents.- 2.5 Methodologies for the preparation of 3-C-methyl branched-chain 3-amino- and 3-nitrosugars of antibiotic substances.- 2.5.1 Cyclization of dialdehyde derivatives with nitroethane.- 2.5.2 Cyanomesylation of hexopyranosid-3-ulose derivatives.- 2.5.3 The spirooxirane route to 3-C-methyl-branched amino- and nitrosugars.- 2.5.4 Addition of iodine azide to C-3 methylene sugars.- 2.5.5 Introduction of the $$\begin{array}{*{20}{c}} {C{{H}_{3}}---} & {\begin{array}{*{20}{c}} | \\ {\text{C}} \\ | \\ \end{array} } & {---{\text{N}}{{{\text{H}}}_{2}}} \\ \end{array}$$ branching by means of I. [3.3]-sigmatropic rearrangement.- 2.6 Subsequent generation of the 2-deoxy functionality of unbranched- and branched-chain 3-aminosugars.- 2.6.1 Deoxygenation of 3-aminohexoses at C-2 according to the Fischer’s glycal procedure.- 2.6.2 Deoxygenation by means of the reductive removal of C-2 thiolester- and thioether functions.- 2.6.3 Reductive dehalogenation of 3-amino-2-halogeno- 2,3-dideoxyhexose derivatives.- 2.7 Synthetic strategies for the preparation of the 6-deoxy analogs of 3-amino-3-deoxyhexopyranosides.- 2.7.1 Deoxygenation at C-6 via C-6 sulfonate ester derivatives.- 2.7.2 C-6 Deoxygenation of 3-azido- and 3-amino-2,3-dideoxyhexopyranosides with the utilization of the ring opening reactions of 4,6-O-benzylidene acetals.- 2.7.3 Miscellaneous methods for the preparation and dehalogenation of 6-halogeno-3-amino- and 3-azidohexopyranosides.- 2.7.4 Preparation of the 6-deoxy analogs of C-3 nitrogen-substituted 2,3-dedeoxyhexopyranosides with concomitant inversion of the configuration at C-5.- 2.8 Interconversion of 3-amino-2,3-dideoxy- and 3-amino- 2,3,6-trideoxyhexose derivatives by means of the inversion of the configuration at carbon C-4.- 2.8.1 The arabino ? lyxo conversion.- 2.8.2 The lyxo ? arabino configurational transformation.- 2.8.3 The ribo ? xylo C-4 configurational inversion.- 2.8.4 The xylo ? ribo configurational step-over.- 2.8.5 Methods for the configurational interchange at the carbohydrate portion of the intact anthracycline antibiotics.- 3. Synthesis of 3-Amino-2,3,6-Trideoxyhexoses by Using Non-carbohydrate Precursors.- 3.1 Synthesis of 3-amino-2,3,6-trideoxyhexoses from six-carbon substrates.- 3.2 Synthesis of 3-amino-2,3,6-trideoxyhexoses from chiral and achiral precursors by means of carbon-carbon bond formation reactions.- 3.2.1 Construction of the six-carbon framework with a 5C + 1C ascent.- 3.2.2 Synthesis of 3-amino-2,3,6-trideoxyhexoses according to the 4C + 2C chain-lengthening principle.- 3.2.3 Construction of the carbon framework of 3-amino-2,3,6-trideoxyhexoses by means of the [4C + 3C]-1C methodology.- 3.2.4 3C + 3C Type construction of 3-amino-2,3,6-trideoxyhexoses.- 3.2.5 Miscellaneous methods.- 4. Miscellaneous Functionalized Derivatives of 3-Amino-3-Deoxyhexoses of Antibiotics and Their Conversion into Other Organic Substances.- 4.1 Thio-, nitrogen-and C-glycosides of 3-amino-2,3,6-trideoxyhexoses.- 4.1.1 1-Thio derivatives.- 4.1.2 Nitrogen-glycoside derivatives of daunosamine.- 4.1.3 C-Glycoside analogs of daunosamine.- 4.2 N-Substituted derivatives of daunosamine-type aminodeoxy hexoses.- 4.3 4-Deoxy-, C-4 branched-chain and other C-4 substituted derivatives of 3-amino-2,3,6-trideoxyhexoses.- 4.3.1 Synthesis of 4-deoxy analogs.- 4.3.2 C-4 Branched-chain derivatives.- 4.3.3 Syntheses of C-4 substituted 3-amino-2,3,6-trideoxyhexoses susceptible of transformations into beta-lactam antibiotic (thienamycin) analogs.- 4.4 Furanose-ring analogs of 3-amino-2,3,6-trideoxyhexoses.- 4.5 Synthesis of the 6-azido- and 6-amino derivatives of 3-amino-di- and trideoxyhexoses.- 4.5.1 6-Azido-and amino analogs of D-ristosamine.- 4.5.2 Approaches to 3,6-diaminohexose precursors for the synthesis of antibiotic negamycin.- 4.6 Synthesis of the uronic acid derivatives of 3-amino-di- and trideoxyhexoses.- 4.7 Conversion of 3-amino- and 3-azido-2,3,6-trideoxyhexose derivatives into carbocyclic compounds.- 5. Concluding Remarks.- Note Added in Proof.- References.
