Chromium(II)-Catalyzed Amination of N-Heterocyclic Chlorides with Magnesium Amides

Andreas K. Steib; Sarah Fernandez; Olesya M. Kuzmina; Martin Corpet; Corinne Gosmini; Paul Knochel

doi:10.1055/s-0034-1380178

Synlett, Inhaltsverzeichnis

Synlett 2015; 26(08): 1049-1054
DOI: 10.1055/s-0034-1380178

letter

Chromium(II)-Catalyzed Amination of N-Heterocyclic Chlorides with Magnesium Amides

Andreas K. Steib

^aDepartment of Chemistry, Ludwig-Maximilians-Universität, Butenandtstr. 5–13, 81377 Munich, Germany eMail: paul.knochel@cup.uni-muenchen.de

,

Sarah Fernandez

^aDepartment of Chemistry, Ludwig-Maximilians-Universität, Butenandtstr. 5–13, 81377 Munich, Germany eMail: paul.knochel@cup.uni-muenchen.de

,

Olesya M. Kuzmina

^aDepartment of Chemistry, Ludwig-Maximilians-Universität, Butenandtstr. 5–13, 81377 Munich, Germany eMail: paul.knochel@cup.uni-muenchen.de

,

Martin Corpet

^bLaboratoire de Chimie Moléculaire, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France eMail: corinne.gosmini@polytechnique.edu

,

Corinne Gosmini

^bLaboratoire de Chimie Moléculaire, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France eMail: corinne.gosmini@polytechnique.edu

,

Paul Knochel*

^aDepartment of Chemistry, Ludwig-Maximilians-Universität, Butenandtstr. 5–13, 81377 Munich, Germany eMail: paul.knochel@cup.uni-muenchen.de

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Abstract

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Abstract

We report a ligand-free chromium(II)-catalyzed amination reaction of various N-heterocyclic chlorides. CrCl₂ regioselectively catalyzes the reaction of chloropyridines and dichloropyridines, dichloroquinolines, dichloroisoquinolines and dichloroquinoxalines with a range of aliphatic, allylic, benzylic and saturated (hetero)cyclic magnesium amides in the presence of lithium chloride as additive. The reactions were performed at 50 °C in THF and led to the desired aminated products in 56–96% yield.

Key words

chromium - amination - magnesium amides - heterocycles - pyridine

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Referenzen

References and Notes

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12 CrCp₂ was purchased from Alfa Aesar (>97% purity) or prepared according to: Rohde W, Goertz H.-H, Handrich U. Ger. Patent DE4337230A1, 1995
13 Cr(acac)₃ was purchased from Sigma Aldrich (97% purity). The air-stable and cheap Cr(acac)₃ could be used in these aminations but led to either similar or, in most cases, to somewhat lower yields and/or longer reaction times.
14 CrBr₂ was prepared according to: Concellón JM, Rodríguez-Solla H, Blanco EG, Villa-García MA, Alvaredo N, García-Granda S, Díaz MR. Adv. Synth. Catal. 2009; 351: 2185
15 However, a longer reaction time (20 h at 50 °C) also led to full conversion.

16a Typical procedure for the Cr-catalyzed amination using CrCl₂ : The previously prepared solution of the magnesium amide was transferred via syringe to a second dry and argon-flushed Schlenk tube, containing water-free CrCl₂ (0.1 equiv) and the N-heterocyclic halide in THF (1 equiv, 2 M in THF) at 23 °C. The resulting reaction mixture was stirred at 50 °C until the N-heterocyclic halide was consumed. The solvent was evaporated in vacuo and the crude product was purified on silica gel to afford the desired product.
16b Typical procedure for the Cr-catalyzed amination using Cr(acac)₃ : The previously prepared solution of the magnesium amide was transferred via syringe to a second dry and argon-flushed Schlenk tube, containing Cr(acac)₃ (0.1 equiv) and the N-heterocyclic halide in THF (1 equiv, 2 M in THF) at 23 °C. The resulting reaction mixture was stirred at 50 °C until the N-heterocyclic halide was consumed. The solvent was evaporated in vacuo and the crude product was purified on silica gel to afford the desired product.

17 No diamination product was observed in the aminations involving 1c, 1d, 1e and 1h.
18 Magnesium chloride indolin-1-ide (2e) reacted rapidly with 1d but the related magnesium chloride methylanilide underwent the amination reaction in only 32% yield, showing the limits of the CrCl₂ catalysis.

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