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This book is an update on development of methodologies towards the synthesis of N-heteroarenes via AlCl3-induced heteroarylation protocol. Undoubtedly, the AlCl3-induced heteroarylation method could be viewed as a useful alternative to the transition metal mediated cross coupling processes such as Suzuki reactions (when applied to a similar type of C-C bond forming reaction) as the protocol avoids cumbersome preparation of boronic acids or other organometallic reagents and formation of homocoupled products as byproducts. For clarity, the book provides an overview of unique methodologies such as AlCl3 induced heteroarylation-cyclization, hydroarylation-heteroarylation, sulfonyl group migration that highlights the use of AlCl3 beyond the famous Friedel-Crafts (FC) alkylation / acylation reactions leading to new N-heteroarenes of biological significance.