NDLI: A synthetic and mechanistic investigation into the cobalt(i) catalyzed amination of aryl halides

Content Provider	Royal Society of Chemistry (RSC)
Author	Brennan, Marshall R. Kim, Dongyoung Fout, Alison R.
Copyright Year	2014
Abstract	Employing first-row transition metals in catalytic two-electron transformations remains a synthetic challenge. In order to overcome the common and often deleterious single-electron reactivity, an electron rich ligand was targeted on cobalt. Herein, we report the Co(I) catalyzed amination of aryl halides with lithium hexamethyldisilazide. This transformation features (PPh3)3CoCl (1) as the catalyst and affords structurally diverse and electronically varied primary arylamines in good chemical yields, with the scope of the reaction featuring arylamines that cannot be synthesized via traditional metal-catalyzed amination routes, including 4-aminophenylboronic acid pinacol ester. Stoichiometric reactivity revealed that (PPh3)2CoN(SiMe3)2 (2) is likely generated within the catalytic cycle and could be independently synthesized from the reaction of (PPh3)3CoCl with LiN(SiMe3)2. Catalytic reactivity featuring the Co–amide complex, (PPh3)2CoN(SiMe3)2, showed that it is a competent catalyst, implying that the (PPh3)3CoCl may be serving as a pre-catalyst in the reaction. Both stoichiometric and kinetic studies support the catalytic cycle involving a Co(I) complex. Catalytic reactions featuring Co(II) complexes resulted in undesired biaryl formation, a product that is not observed under standard catalytic conditions and any productive catalytic reactivity likely arises from an in situ reduction of Co(II) to Co(I). A Hammett study was carried out to differentiate between a closed-shell or radical mechanism, the results of which are consistent with the proposed closed-shell mechanism. Initial studies indicate that this reactivity may be expanded to other bulky nucleophiles.
Starting Page	4831
Ending Page	4839
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	12
Journal	Chemical Science
DOI	10.1039/c4sc01257g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Ester Stoichiometry Hammett Ligand Carboxylic acid Hammett equation Aryl This Transformation Cobalt Lithium bis(trimethylsilyl)amide Pinacol Catalytic cycle
Content Type	Text
Resource Type	Article
Subject	Chemistry

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