1;Science of Synthesis Knowledge Updates 2016/3;1 2;Title Page;6 3;Copyright;8 4;Preface;9 5;Abstract;11 6;Science of Synthesis Knowledge Updates 2016/3;13 7;Table of Contents;15 8;10.22 Product Class 22: Azaindoles and Their Derivatives;23 9;10.22.1 Product Subclass 1: Azaindoles;23 9.1;10.22.1.1 Synthesis by Ring-Closure Reactions;34 9.1.1;10.22.1.1.1 By Annulation to a Pyridine;34 9.1.1.1;10.22.1.1.1.1 By Formation of One N-C and One C-C Bond;34 9.1.1.1.1;10.22.1.1.1.1.1 With Formation of 1-2 and 3-3a Bonds;34 9.1.1.1.1.1;10.22.1.1.1.1.1.1 Method 1: From Pyridylhydrazones (Fischer Synthesis);34 9.1.1.1.1.1.1;10.22.1.1.1.1.1.1.1 Variation 1: Indolization with Pyridinium Hydrochloride;39 9.1.1.1.1.1.2;10.22.1.1.1.1.1.1.2 Variation 2: From (6-Methoxypyridin-3-yl)hydrazine or (2-Methoxypyridin- 3-yl)hydrazine;40 9.1.1.1.1.1.3;10.22.1.1.1.1.1.1.3 Variation 3: Using Microwave Activation;44 9.1.1.1.1.1.4;10.22.1.1.1.1.1.1.4 Variation 4: From a Pyridin-4-yldiazonium N-Oxide and a ?-Oxo Acid;45 9.1.1.1.1.1.5;10.22.1.1.1.1.1.1.5 Variation 5: From a Pyridylhydrazine and an Enamine;46 9.1.1.1.1.1.6;10.22.1.1.1.1.1.1.6 Variation 6: From a Pyridylhydrazine and a ?-Halo Ketone (Grandberg Synthesis);47 9.1.1.1.1.1.7;10.22.1.1.1.1.1.1.7 Variation 7: From 4-Hydrazino-6-methylpyridin-2(1H)-one;48 9.1.1.1.1.1.8;10.22.1.1.1.1.1.1.8 Variation 8: From a Pyridylboronic Acid and Di-tert-butyl Azodicarboxylate;49 9.1.1.1.1.2;10.22.1.1.1.1.1.2 Method 2: From ortho-Substituted Nitropyridines (Bartoli Synthesis);53 9.1.1.1.1.3;10.22.1.1.1.1.1.3 Method 3: From N-Chloropyridin-2-amines and ?-Alkylsulfanyl Ketones (Gassman Synthesis);57 9.1.1.1.1.4;10.22.1.1.1.1.1.4 Method 4: From Pyridinamines and ?-Hydroxy Ketones (Bischler Synthesis);58 9.1.1.1.1.5;10.22.1.1.1.1.1.5 Method 5: From Halopyridin-2-amines and Alkynes (Larock Synthesis);62 9.1.1.1.1.6;10.22.1.1.1.1.1.6 Method 6: From Enamines of Pyridyl Ketones/Aldehydes;74 9.1.1.1.1.7;10.22.1.1.1.1.1.7 Method 7: From Iodopyridinamines and Allyl Acetate;78 9.1.1.1.1.8;10.22.1.1.1.1.1.8 Method 8: From Nitropyridines and Alkynes;80 9.1.1.1.2;10.22.1.1.1.1.2 With Formation of 1-2 and 2-3 Bonds;81 9.1.1.1.2.1;10.22.1.1.1.1.2.1 Method 1: From an Alkyl-N-(tert-Butoxycarbonyl)pyridinamine and an Amide;81 9.1.1.1.2.1.1;10.22.1.1.1.1.2.1.1 Variation 1: From an Unprotected Alkylpyridinamine and an Ester;89 9.1.1.1.2.2;10.22.1.1.1.1.2.2 Method 2: From a 2-Aminopyridine-3-carbaldehyde and a Diazo Ester;90 9.1.1.1.2.3;10.22.1.1.1.1.2.3 Method 3: From a Methylpyridinamine and the Vilsmeier Reagent;91 9.1.1.1.3;10.22.1.1.1.1.3 With Formation of 1-7a and 2-3 Bonds;92 9.1.1.1.3.1;10.22.1.1.1.1.3.1 Method 1: From an Alkylpyridine and a Nitrile;92 9.1.1.1.3.1.1;10.22.1.1.1.1.3.1.1 Variation 1: From a 2-Fluoro(alkyl)pyridine and a Nitrile;93 9.1.1.1.3.2;10.22.1.1.1.1.3.2 Method 2: From a 2-(2-Chloropyridin-3-yl)oxirane and an Amine;94 9.1.1.1.3.3;10.22.1.1.1.1.3.3 Method 3: From a 2-Halopyridyl Aldehyde and Ethyl Isocyanoacetate;96 9.1.1.1.4;10.22.1.1.1.1.4 With Formation of 1-2 and 1-7a Bonds;97 9.1.1.1.4.1;10.22.1.1.1.1.4.1 Method 1: From a 2-Chloro-3-(2-chloroethyl)pyridine and an Amine;97 9.1.1.1.4.1.1;10.22.1.1.1.1.4.1.1 Variation 1: From 3-(2-{[(Trifluoromethyl)sulfonyl]oxy}ethyl)pyridine- 2,6-diyl Bis(trifluoromethanesulfonate) and an Amine;99 9.1.1.1.4.2;10.22.1.1.1.1.4.2 Method 2: From a 2-Bromo-3-(2-bromoalkenyl)pyridine and an Amine;101 9.1.1.1.4.3;10.22.1.1.1.1.4.3 Method 3: From a 2-Alkynyl-3-bromopyridine and a Carbamate;103 9.1.1.2;10.22.1.1.1.2 By Formation of One N-C Bond;103 9.1.1.2.1;10.22.1.1.1.2.1 With Formation of the 1-2 Bond;103 9.1.1.2.1.1;10.22.1.1.1.2.1.1 Method 1: From (3-Nitropyridin-2-yl)pyruvates (Reissert Synthesis);103 9.1.1.2.1.2;10.22.1.1.1.2.1.2 Method 2: From a Halopyridinamine and an Enolate;111 9.1.1.2.1.3;10.22.1.1.1.2.1.3 Method 3: From Alkynylpyridinamines;114 9.1.1.2.1.3.1;10.22.1.1.1.2.1.3.1 Variation 1: Base-Mediated Cyclization;114 9.1.1.2.1.3.2;10.22.1.1.1.2.1.3.2 Variation 2: Usi