Despite recent developments, selective C(sp3)-H borylation of feedstock amines remains a formidable challenge. Herein, we have developed a general, mild, and photoinduced transition metal- and strong base-free method for α-C(sp3)-H borylation of amines. This protocol features a regioselective 1,5-hydrogen atom transfer process to access key α-aminoalkyl radical intermediate using commercially available easy-to-install/remove iodobenzoyl radical translocating group. Remarkably, this general, efficient, and operationally simple method allows activation of primary and secondary α-C-H sites of a broad range of acyclic and cyclic amines toward highly regio- and diastereoselective synthesis of valuable α-aminoboronates. Utility of this protocol has been demonstrated by its employment in late-stage borylation of structurally complex amines and formal C-H arylation reaction of amines. Thus, it is expected that this operationally simple, general, and practical method will find broad application in organic synthesis and drug discovery. 

General and Selective Metal-Free Radical α-C-H Borylation of Aliphatic Amines.

This review aims to provide a comprehensive overview of condensation-based methods for the C–H bond functionalization of amines that feature azomethine ylides as key intermediates. These transformations are typically redox-neutral and share common attributes with classic name reactions such as the Strecker, Mannich, ­Friedel–Crafts, Pictet–Spengler, and Kabachnik–Fields reactions, while incorporating a redox-isomerization step. This approach provides an ideal platform to rapidly transform simple starting materials into complex amines. 1 	Introduction 1.1 	General Remarks 1.2 	Overview 1.3 	Scope of This Review 2 	Aromatization of Cyclic Amines 2.1 	Pyridines from Piperidine 2.2 	Isoquinolines from Tetrahydroisoquinolines and Quinolines from Tetrahydroquinolines 2.3 	Pyrroles from 3-Pyrroline or Pyrrolidine 2.4 	Indoles from Indolines 3 	Pericyclic Reactions 3.1 	(3+2)-Dipolar Cycloadditions 3.2 	6π-Electrocyclizations 3.3 	1,5-Proton Shifts 4 	Redox-Variants of Classic Transformations Incorporating a C–H Bond Functionalization Step 4.1 	α-Cyanation 4.2 	α-Alkynylation 4.3 	α-Phosphonation 4.4 	α-Arylation 4.5 	α-Alkylation with Ketones 4.6 	Redox-Ugi Reaction 4.7 	Miscellaneous Intermolecular Reactions 5 	Redox-Annulations 6 	Reactions Involving β-C–H Bond Functionalization 7 	Outlook

Condensation-Based Methods for the C–H Bond Functionalization of Amines

An unprecedented redox-neutral annulation reaction of tertiary anilines with electron-deficient alkynes was developed that proceeds through a cascade Friedel-Crafts alkylation/[1,5]-hydride transfer/Mannich cyclization sequence. Under B(C6F5)3 catalysis, a range of functionalized 1,2,3,4-tetrahydroquinolines were facilely constructed in moderate to good yields with exclusive 3,4-anti-stereochemistry. The commercial availability of the catalyst and the high atom and step economy of the procedure, together with metal-free and external oxidant-free conditions, make this an attractive method in organic synthesis. 

Borane-catalyzed cascade Friedel–Crafts alkylation/[1,5]-hydride transfer/Mannich cyclization to afford tetrahydroquinolines

Herein, we report a polar-radical relay strategy for α-C-H amination of cyclic amines with N-chloro-N-sodio-carbamates. The relay is initiated by in situ generation of cyclic iminium intermediate using N-iodosuccinimide (NIS) oxidant as an initiator, which then operates through a series of polar (addition and elimination) and radical (homolysis, hydrogen- and halogen atom transfer) reactions to enable the challenging C-N bond formation in a controlled manner. A broad range of α-amino cyclic amines were readily accessed with excellent regioselectivity, and the superb applicability was further demonstrated by functionalization of biologically relevant compounds.

Photoinduced α-C-H Amination of Cyclic Amine Scaffolds Enabled by Polar-Radical Relay.

N-dealkylation, the removal of an N-alkyl group from an amine, is an important chemical transformation which provides routes for the synthesis of a wide range of pharmaceuticals, agrochemicals, bulk and fine chemicals. N-dealkylation of amines is also an important in vivo metabolic pathway in the metabolism of xenobiotics. Identification and synthesis of drug metabolites such as N-dealkylated metabolites are necessary throughout all phases of drug development studies. In this review, different approaches for the N-dealkylation of amines including chemical, catalytic, electrochemical, photochemical and enzymatic methods will be discussed.

/pdf/n-dealkylation-of-amines-h5aowhbt.pdf

N-Dealkylation of Amines

α,α'-C-H Bond Difunctionalization of Unprotected Alicyclic Amines.

This Graphical Review provides a concise overview of the manifold and mechanistically diverse methods that enable the functionalization of sp3 C–H bonds in amines and their derivatives.

/pdf/c-h-bond-functionalization-of-amines-a-graphical-overview-of-15v7petwik.pdf

C-H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods.

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α,α'-C-H Bond Difunctionalization of Unprotected Alicyclic Amines.

C-H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods.