Copper Catalyzed Enantioselective Intramolecular Aminooxygenation of Alkenes

This Perspective describes the development of a family of copper(II)-catalyzed alkene difunctionalization reactions that enable stereoselective addition of amine derivatives and alcohols onto pendant unactivated alkenes to provide a range of valuable saturated nitrogen and oxygen heterocycles. 2-Vinylanilines and related substrates undergo alternative oxidative amination or allylic amination pathways, and these reactions will also be discussed. The involvement of both polar and radical steps in the reaction mechanisms have been implicated. Major product formation is a function of the lowest energy pathway, which in turn is a function of structural aspects of the various reaction components.

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“…42–44 Sulfonamides demonstrated the most promising properties with respect to reactivity and enantioselectivity. On small scale (ca.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective and Regioselective Synthesis of Heterocycles via Copper-Catalyzed Additions of Amine Derivatives and Alcohols to Alkenes

2017

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“…[51] The first intramolecular enantioselective oxyamination reaction was reported by Chemler in 2008. [54] In this publication, a range of sulfonamides were cyclised in good yields with excellent regioselectivity onto tethered, terminal alkenes in the presence of a catalytic loading of copper(II) salts (Scheme 32). 2,2',6,6',-Tetramethylpiperidine (TEMPO) is present as both the stoichiometric reoxidant and the oxygen source.…”

Section: Copper-mediated Reactionsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

267

116

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1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.

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“…The combination of Cu(OTf ) 2 /(4R,5S)-bis-Phbox ligand is crucial for this reaction and moderate to excellent enantioselectivity could be obtained. The primary carbon radical species generated from the intramolecular amination via C-H activation could be trapped with tetramethylaminopyridyl radical (TEMPO) to give the aminooxygenation product [57]. They also disclosed that the reaction is first order both in substrate and the [Cu(R,R)-Ph-bis(oxazoline)]OTf2 catalyst and zero order in TEMPO via kinetics studies.…”

Section: Copper-catalyzed Synthesis Of Indolinesmentioning

confidence: 99%