Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors

Pichon, Delphine; Morvan, Jennifer; Crévisy, Christophe; Mauduit, Marc

doi:10.3762/bjoc.16.24

Cited by 17 publications

(8 citation statements)

References 54 publications

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“…Over a century has already passed since the first copper-catalyzed reaction was reported, and copper-catalyzed reactions are still broadly used among chemistry laboratories all over the world. ,− This can be illustrated by a Scifinder query search of the last three decades for the term “copper-catalyzed”. For the 1990s, 439 results are given; there were almost 2,000 hits in the 2000s, and the number has continued to grow with, as this review is drafted, the number being almost 7,000.…”

Section: Copper-catalyzed C–b Bond Formationmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon−boron bond into a carbon−X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row dblock transition metals have become increasingly widely used as catalysts for the formation of a carbon−boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon−boron bonds.

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Section: Copper-catalyzed C–b Bond Formationmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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“…The introduction of a methyl group, despite its small size and simplicity, can induce profound changes in the properties of a molecule. − In biologically active compounds, the incorporation of a methyl group may result in conformational changes which increase the structural complementarity of a lead compound to its target receptor with minimal impact on its molecular weight and lipophilicity (Figure A). − While common approaches for the introduction of other single-carbon fragments rely on the asymmetric functionalization of olefins, − few strategies have been reported for the direct installation of methyl groups. Standard methods to directly install methyl groups rely on conjugate additions to polarized olefins using preformed organometallic reagents facilitated by chiral Lewis acid catalysts. − …”

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confidence: 99%

Copper Hydride-Catalyzed Enantioselective Olefin Hydromethylation

et al. 2022

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The enantioselective installation of a methyl group onto a small molecule can result in the significant modification of its biological properties. While hydroalkylation of olefins represents an attractive approach to introduce alkyl substituents, asymmetric hydromethylation protocols are often hampered by the incompatibility of highly reactive methylating reagents and a lack of general applicability. Herein, we report an asymmetric olefin hydromethylation protocol enabled by CuH catalysis. This approach leverages methyl tosylate as a methyl source compatible with the reducing base-containing reaction environment, while a catalytic amount of iodide ion transforms the methyl tosylate in situ into the active reactant, methyl iodide, to promote the hydromethylation. This method tolerates a wide range of functional groups, heterocycles, and pharmaceutically relevant frameworks. Density functional theory studies suggest that after the stereoselective hydrocupration, the methylation step is stereoretentive, taking place through an S N 2-type oxidative addition mechanism with methyl iodide followed by a reductive elimination.

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“…Traditional methods involved organometallic, two-electron, conjugate addition reactions onto electron-deficient olefins (Michael acceptors), but these organometallic reagents were often toxic, difficult to prepare and/or unstable, thus limiting their applicability. 2 Recent decades have witnessed the extensive utility of Giese-type 3 reactions involving additions of radical intermediates onto versatile Michael acceptors, allowing scope expansion to secondary, tertiary, or heteroatom-stabilised substrates as suitable coupling partners.…”

Section: Introductionmentioning

confidence: 99%