Chemistry of thioamides
- Toshiaki Murai, editor.
- Singapore : Springer, 2019.
- Physical description
- 1 online resource
- Murai, Toshiaki, editor.
- Includes bibliographical references.
- Intro; Preface; Contents; 1 Thioamides: Overview; References; 2 Theoretical Aspects of Thioamides; 2.1 Basic Structural Features of Thioamides; 2.1.1 Planarity of Thioamides; 2.1.2 Derivations from Planarity; 2.2 Tautomerization; 2.3 Rotations Around the C-N Amide Bond; 2.3.1 Simple Examples; 2.3.2 Solvent Effects; 2.3.3 Influence of Remote Substituents; 2.3.4 Photoisomerization; 2.3.5 C-N Bond Rotation in Complex Systems; 2.4 Rotational Barriers of N-Substituents; 2.5 Conjugation with Different Substituents; 2.6 Thiopeptides; 2.7 N-H Bond Dissociation Enthalpy (BDE); 2.8 Others
- 2.9 ConclusionsReferences; 3 Synthesis of Thioamides; 3.1 Introduction; 3.2 The Direct Incorporation of Elemental Sulfur; 3.2.1 Combination of Ketones, Amines, and Elemental Sulfur; 3.2.2 Combination of Aldehydes, Amines, and Elemental Sulfur; 3.2.3 Combination of Carboxylic Acids, Amines, and Elemental Sulfur; 3.2.4 Combination of Amines and Elemental Sulfur; 3.2.5 Combination of Alkynes, Amines, and Elemental Sulfur; 3.2.6 Combination of Benzylic Halides, Amines, and Elemental Sulfur; 3.2.7 Combination of Methyl Heteroarenes, N, N-Dimethyl Formamide, and Elemental Sulfur
- 3.3 Thionation of Amides3.3.1 Thionating Agents having P=S Bonds; 3.3.2 Thionation of Amides with Elemental Sulfur and Hydrochlorosilanes; 3.3.3 Thionation of Amides with Rhodanine; 3.4 Addition of Thionating Agents to Nitriles; 3.5 Thiocarbonyl Compounds as a Starting Material; 3.5.1 Addition to Isothiocyanates; 3.5.2 Addition to Other Thiocarbonyl Compounds; 3.6 Thiols, Sodium Sulfides, and Disulfide as a Sulfur Source; 3.7 Summary; References; 4 Reaction of Thioamides; 4.1 Introduction; 4.2 Oxidation of Thioamides; 4.3 Reaction at the Nitrogen Atom of Thioamides
- 5.1 Introduction5.2 Enantioselective Reactions Using Thioamides; 5.2.1 Auxiliary Approach; 5.2.2 Chiral Lewis Acid Approach; 5.3 Catalytic Enantioselective Reactions of Thioamides; 5.3.1 Use of Thioamides as Pronucleophiles; 5.3.2 Use of Thioamides as Electrophiles; 5.4 Utility in Enantioselective Synthesis of Natural Products and Biologically Active Compounds; 5.5 Future Outlook; References; 6 Synthesis of Heterocycles from Thioamides; 6.1 Introduction; 6.2 Synthesis of Heterocycles with One Heteroatom; 6.2.1 S-Heterocycles; 6.2.2 N-Heterocycles; 6.3 Heterocycles with Two Heteroatoms
- This book covers whole aspects of the sulfur isologues of amides. Starting from the synthetic methods of thioamides, a range of synthetic applications to the construction of carbon–sulfur and carbon–carbon bonds, to asymmetric reactions, to formation of heterocycles are described. Among the array of thiocarbonyl compounds, thioamides are readily handled in room temperature air. Some of their characteristic features are that the polarity of C=S bonds in thioamides is much smaller than C=O bonds in ordinary amides, that thioamides possess higher HOMO and lower LUMO when compared with those of ordinary amides, and that carbon atoms alpha to the C=S and nitrogen atoms in thioamides are more acidic than those in ordinary amides. Theoretical studies further disclose their features. Thioamides are also used as ligands to a wide variety of metals. Their unique photophysical properties and catalytic activities are described here. Characteristic features of biologically relevant thioamides, e.g., thiopeptides and related compounds, are the final focus of the book.
- Publication date
- 9789811378287 (electronic bk.)
- 9811378282 (electronic bk.)