Metal-Initiated Amination of Alkenes and Alkynes

Abstract

ContentsI. Introduction 675 II. Mechanism and Coordination Chemistry 676 1. Activation of the Olefin 677 a. Stoichiometric Use of Transition Metals 677 b. Making the Reaction Catalytic 679 2. N−H Activation by Alkali Metals 680 3. Activation of the N−H Bond by Early Transition Metals, Lanthanides, and Actinides 681 4. Activation of the N−H Bond by Late Transition Metals 684 III. Synthetic Applications of Catalytic Aminations 686 1. Aminations Catalyzed by Zeolites 686 2. Aminations Assisted by Alkali Metals 686 a. Ethylene 686 b. Aliphatic Olefins 687 c. Styrenes 688 d. 1,3-Butadienes 689 3. Aminations Catalyzed by Transition Metals 690 a. Palladium-Catalyzed Aminations of Olefins 690 b. Other Catalytic Oxidative Aminations of Olefins 693 c. Amination of Allenes 693 d. Intramolecular Amination of Alkynes 694 e. Intramolecular Amination of Alkenes 695 f. Tandem Cyclization Reactions of Aminoalkynes and -alkenes 697 g. Intermolecular Hydroamination Reactions 698 IV. Summary and Conclusions 699 V. Acknowledgments 700 VI. References 700

Hydroaminomethylation of high alkenes with dual-metal catalysts in aqueous/organic biphasic system

“…This could be explained by the view that the further increase of CTAB concentration could induce the micelle to expand and even to form an O/W micro-emulsion in the presence of polar organic compounds. 11 As shown in Table 3, with the increase of molar ratio of phosphine to metal, both the conversion of 1-dodecene and selectivity for amine increased initially and then decreased, while the regioselectivity for linear product increased continually (entries [1][2][3][4][5]. This could be attributed to the ratio of phosphine ligand (L) to metal (M = Rh, Ir) affecting the coordination equilibrium of catalytic active species.…”

“…The traditional synthetic routes to long-chain amines are mostly multi-step-and less atom-efficient-processes, with a number of by-products. 1,2 The hydroaminomethylation of alkenes has recently attracted great attention as an atom-economically efficient one-pot synthesis of amines. The hydroaminomethylation of high alkenes in homogeneous catalysis has been investigated by Schultes 3 using the Rh/Ru catalyst.…”

Homogeneous gold catalysts and alkynes: A successful liaison

“…Both types of heterocycles are frequently found in natural products, and Utimoto also used this methodology for the synthesis of some natural products. Gold complexes still range among the most effective catalysts for the intramolecular amination of triple bonds (23), especially because unlike with the newer lanthanoide catalysts (where one often has to work in a glove-box!) (24,25), it is not necessary to thoroughly exclude humidity and oxygen, the gold-catalysts are quite robust.…”

Palladium Complex Bearing 3,5-Bis(benzotriazol-1-Ylmethyl)toluene Ligand Catalyzes Oxidative Amination of Allyl Butyl Ether

“…This assumption is supported by the presence of one band at 350 cm -1 in the infrared spectrum, assigned to the stretching frequency of the Pd-Cl bond, which is characteristic of a trans dichloride isomer. 40 Considering that a variety of palladium(II) complexes have been successfully studied as catalysts in oxidative amination of alkenes reactions, [25][26][27][28][29][30][31][32][33][34][35][36][37] we tested the behavior of complexes 2 and 3 in the reaction of phthalimide with allyl butyl ether.…”

“…24 On the other hand, a variety of palladium(II) complexes have been successfully studied as catalysts for the aerobic oxidative amination of unactivated alkenes to yield amine derivatives. [25][26][27][28][29][30][31][32][33][34][35][36][37][38] This catalytic reaction leads to the formation of imines or enamines, via b-hydride elimination, through a mechanism analogous to the well-known Wacker process. 25 In this communication we report the synthesis and characterization of the new ligand 3,5-bis(benzotriazol-1-ylmethyl)toluene (1) …”