Copper-Catalyzed Enantioselective Formal Hydroamination of Oxa- and Azabicyclic Alkenes with Hydrosilanes and Hydroxylamines

Miki, Yuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

doi:10.1021/ol5003219

Cited by 114 publications

(44 citation statements)

References 80 publications

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“…[37] This transformation was also applicable for oxa-and azabicyclic alkenes [38] and alkenyl dan boronates. [37] This transformation was also applicable for oxa-and azabicyclic alkenes [38] and alkenyl dan boronates.…”

Section: Cu-h Catalyzed Hydroaminationmentioning

confidence: 99%

Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

2018

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Hydrometallation of alkenes and alkynes provides a straightforward route to access alkyl-or alkenyl-metal reagents, which have a wide range of applications in organic transformations. In recent years, the first row transition metals (such as copper, nickel, cobalt, iron, etc.) have emerged high activity and selectivity in this area with the aid of a variety of ligands. This review covers the recent advances in the hydrometallation of minimally functionalized unsaturated C-C bonds (including alkenes, alkynes, dienes, allenes, enynes, etc.), as well as transformations involving catalytic hydrometallation process via the first row transition metal catalysis.

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Section: Cu-h Catalyzed Hydroaminationmentioning

confidence: 99%

Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

2018

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“…[28] In the reported process, the optimal catalyst was found to be a combination of CuCl and ( R , R )-Ph-BPE (L5). The enantioselectivities obtained ranged from moderate to excellent and a wide range of amine electrophiles, including one derived from the hindered 2,2,6,6-tetramethylpiperidine, could be successfully employed.…”

Section: Copper(i) Hydride-catalyzed Hydroamination – Discovery Smentioning

confidence: 99%

Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes

2015

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Over the past few years, CuH-catalyzed hydroamination has been discovered and developed as a robust and conceptually novel approach for the synthesis of enantioenriched secondary and tertiary amines. The success in this area of research was made possible through the large body of precedent in copper(I) hydride catalysis and the well-explored use of hydroxylamine esters as electrophilic amine sources in related copper-catalyzed processes. This mini-review details the background, advances, and mechanistic investigations in CuH-catalyzed hydroamination.

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“…In particular, while the reduction of ketone 1 with a catalyst generated from DTBM-SEGPHOS indeed requires a low activation energy (Δ G ‡ ) of 9.9 kcal/mol, the same process is less facile when other commercially available ligands are employed. In particular, the use of a catalyst derived from Ph-BPE ( L2 ), another ligand previously employed in CuH chemistry (20, 34), results in a higher activation energy (Δ G ‡ = 13.6 kcal/mol). Furthermore, calculations suggested that the activation barrier for the hydrocupration of enyne 3 is 1.3 kcal/mol lower than that of ketone 1 with this Ph-BPE-based catalyst, indicating the feasibility of chemoselective enyne hydrocupration in the presence of ketones.…”

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confidence: 99%

Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones

Yang

Perry

Lü

et al. 2016

Science

255

134

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Enantioenriched alcohols found in an array of bioactive natural products and pharmaceutical agents are often synthesized by asymmetric nucleophilic addition to carbonyls. However, this approach generally shows limited functional group compatibility, requiring the use of preformed organometallic reagents in conjunction with a stoichiometric or sub-stoichiometric amount of chiral controller to deliver optically active alcohols. Herein we report a copper-catalyzed strategy for the stereoselective nucleophilic addition of propargylic and other alkyl groups to ketones using easily accessible (poly)unsaturated hydrocarbons as latent carbanion equivalents. Our method features the catalytic generation of highly enantioenriched organocopper intermediates and their subsequent diastereoselective addition to ketones, allowing for the effective construction of highly substituted stereochemical dyads with excellent stereocontrol. Moreover, this process is general, scalable, and occurs at ambient temperature.

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Copper-Catalyzed Enantioselective Formal Hydroamination of Oxa- and Azabicyclic Alkenes with Hydrosilanes and Hydroxylamines

Cited by 114 publications

References 80 publications

Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

Recent Advances in Hydrometallation of Alkenes and Alkynes via the First Row Transition Metal Catalysis

Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes

Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones

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