Catalytic Asymmetric Cross‐Couplings of Racemic α‐Bromoketones with Arylzinc Reagents

Lundin, Pamela M.; Esquivias, Jorge; Fu, Gregory C.

doi:10.1002/anie.200804888

Cited by 150 publications

(52 citation statements)

References 27 publications

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“…10,11 We have now begun to explore enantioselective couplings of other families of electrophiles, beginning with geminal dihalides (eq 1; Z = F, X = halide); 12 such H → F substitutions can have a dramatic impact on reactivity and/or ee. 13 If a suitable catalyst could achieve selective cleavage of the C–X bond, along with efficient and highly enantioselective C–C bond formation, then this would enable the catalytic asymmetric synthesis of tertiary alkyl fluorides.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones

Liang

2014

J. Am. Chem. Soc.

169

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The development of new approaches to the construction of fluorine-containing target molecules is important for a variety of scientific disciplines, including medicinal chemistry. In this Article, we describe a method for the catalytic enantioselective synthesis of tertiary alkyl fluorides through Negishi reactions of racemic α-halo-α-fluoroketones, which represents the first catalytic asymmetric cross-coupling that employs geminal dihalides as electrophiles. Thus, selective reaction of a C–Br (or C–Cl) bond in the presence of a C–F bond can be achieved with the aid of a nickel/bis(oxazoline) catalyst. The products of the stereoconvergent cross-couplings, enantioenriched tertiary α-fluoroketones, can be converted into an array of interesting organofluorine compounds.

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Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones

Liang

2014

J. Am. Chem. Soc.

169

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“…4 Recently, we questioned whether enolizable α-aryl aldehydes might also be enantioselectively created and retained via a novel, tandem catalysis mechanism that employs diaryliodonium salts as an arylation partner in the presence of both amine and metal catalysts. 5 Herein, we describe the successful execution of these ideals and present an operationally trivial, room temperature protocol that is sufficiently mild to generate α-carbonyl benzylic stereogenicity without post-reaction racemization (eq 2).…”

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confidence: 99%

Enantioselective α-Arylation of Aldehydes via the Productive Merger of Iodonium Salts and Organocatalysis

2011

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The enantioselective α-arylation of aldehydes has been accomplished using diaryliodonium salts and a combination of copper and organic catalysts. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-formyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. As one example, this new asymmetric protocol has been applied to the rapid synthesis of (S)-ketoprofen, a commercially successful oral and topical analgesic.

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“…[39] For the enantioselective coupling with arylzinc reagents as the nucleophiles, the use of chiral Pybox ligands also depends on the electrophilic substrates. For example, for the Ni-catalyzed reaction of racemic α-bromoketones with arylzinc compounds, 46 is the best ligand, [40] whereas for the reaction of racemic propargylic halides with arylzinc compounds, 47 is the best ligand. [41] Scheme 12.…”

Section: Negishi Reactionsmentioning

confidence: 99%

“…[49] The catalytic activity was improved by employing the modified complex 51 as a catalyst (Scheme 17), which catalyzes the coupling of aryl and heteroaryl halides efficiently: 2 mol-% of 51, with 10 mol-% PPh 3 as an additive, lead to cross-coupling products in excellent yields (Table 11). [40] Scheme 17. CNC-pincer-nickel complexes 49-51.…”

Section: Suzuki Reactionsmentioning

confidence: 99%

Nickel‐Catalyzed Cross‐Coupling with Pincer Ligands

Wang

Liu

2012

Eur J Inorg Chem

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Transition‐metal‐catalyzed cross‐coupling reactions are powerful tools for constructing carbon–carbon and carbon–heteroatom bonds. In this microreview we summarize the nickel‐catalyzed cross‐coupling reactions with pincer ligands. The reactions presented here include Kumada, Negishi, Suzuki, and Sonogashira reactions for the formation of different types of C–C bonds, as well as the thiolation of aryl iodides.

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Catalytic Asymmetric Cross‐Couplings of Racemic α‐Bromoketones with Arylzinc Reagents

Cited by 150 publications

References 27 publications

Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones

Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic α,α-Dihaloketones

Enantioselective α-Arylation of Aldehydes via the Productive Merger of Iodonium Salts and Organocatalysis

Nickel‐Catalyzed Cross‐Coupling with Pincer Ligands

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