Copper-Catalyzed Enantioselective Intramolecular Alkene Amination/Intermolecular Heck-Type Coupling Cascade

Liwosz, Timothy W.; Chemler, Sherry R.

doi:10.1021/ja211272v

Cited by 180 publications

(76 citation statements)

References 48 publications

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“…In the context of copper-catalyzed heterocycle synthesis, we have explored both doubly intramolecular 48–51 and intra-/intermolecular 52 carboamination approaches.…”

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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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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“…In the context of copper-catalyzed heterocycle synthesis, we have explored both doubly intramolecular 48–51 and intra-/intermolecular 52 carboamination approaches.…”

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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“…10a Sulfonamides 6a and 6b were synthesized as previously reported. 10,27 Characterization data for pyrrolidine 7a has been reported. 10a The synthesis of sulfonamide 6-[D] and the characterization data for indolines 7-[D] have been reported.…”

Section: Methodsmentioning

confidence: 99%

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

2012

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The catalytic asymmetric aminooxygenation of alkenes provides an efficient and straightforward approach to prepare chiral vicinal amino alcohols. We have reported a copper(II)-catalyzed enantioselective intramolecular alkene aminooxygenation, using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as the oxygen source, which results in the synthesis of chiral indolines and pyrrolidines. Herein we disclose that kinetics studies indicate the reaction is first order both in substrate and the [Cu(R,R)-Ph-bis(oxazoline)]OTf2 catalyst, and zero order in TEMPO. Furthermore, kinetic isotope effect studies support that the cis aminocupration step, the addition of N-Cu across the alkene, is the rate-limiting step. Subsequent formation of a carbon radical intermediate, and direct carbon radical trapping with TEMPO is the indicated mechanism for the C-O bond formation as suggested by a deuterium labeling experiment. A ligand screen revealed that C(4)-phenyl substitution on the bis(oxazoline) is optimal for high asymmetric induction. The size of the substrate’s N-sulfonyl group also influences the enantioselectivity of the reaction. The preparative scale catalytic aminooxygenation reaction (gram scale) was demonstrated and an unexpected dependence on reaction temperature was uncovered on the larger scale reaction.

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“…In 2012, Chemler and co-workers reported that a chiral b-aminoalkyl radical could be generated from an enantioselective aminocupration of a g-aminoalkene followed by C-Cu(II) homolysis (Scheme 17). 22 The generated radical could undergo direct alkenylation under oxidative conditions. Cu(OTf) 2 in combination with a chiral bisoxazoline was applied as the catalyst system and MnO 2 was used as the oxidant.…”

Section: Scheme 14mentioning

confidence: 99%

Olefinic C–H functionalization through radical alkenylation

et al. 2015

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Direct olefinic C-H functionalization represents the ideal way of introducing an alkenyl group into organic molecules. A well-known process is the Heck reaction, which involves alkene insertion and β-hydride elimination in the presence of a transition metal. However, the traditional Heck reaction mainly deals with the alkenylation of aryl or vinyl electrophiles. Recent developments have revealed that alkenylation can also be achieved through radical addition to alkenes and following single-electron-transfer (SET) oxidation/elimination. The radical alkenylation pathway allows alkenylation with a variety of carbon-centered radicals and even heteroatom-centered radicals. This tutorial review gives an overview of recent advances in this emerging field.

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Copper-Catalyzed Enantioselective Intramolecular Alkene Amination/Intermolecular Heck-Type Coupling Cascade

Cited by 180 publications

References 48 publications

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

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

Mechanistic Analysis and Optimization of the Copper-Catalyzed Enantioselective Intramolecular Alkene Aminooxygenation

Olefinic C–H functionalization through radical alkenylation

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