Direct use of 1,3-dienes for the allylation of ketones <i>via</i> catalytic hydroindation

Suzuki, Itaru; Yagi, Kensuke; Miyamoto, Shingo; Shibata, Ikuya

doi:10.1039/d0ra00853b

Cited by 3 publications

(3 citation statements)

References 46 publications

(15 reference statements)

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“…A range of such reactivity has been investigated with aldehyde (or masked-aldehyde) coupling partners, initially by Mori 5 and Le Gendre and Moïse 6 before being extensively developed by the groups of Krische [7][8][9][10][11][12][13] and others 14,15 as a contemporary revolution of classical allylation chemistry. However, ketones remain challenging in all but a few limited cases (see below), 16 likely due to their lower electrophilicity and increased steric demands relative to aldehydes.…”

Section: Introductionmentioning

confidence: 99%

Dual-Catalysed Intermolecular Reductive Coupling of Dienes and Ketones

Mayerhofer,

Lippolis,

Teskey

2023

Preprint

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We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation of a cobalt hydride species and single-electron-reduction of ketones. Subsequent selective hydrogen-atom-transfer from the cobalt hydride generates an allylic radical which can selectively couple with the persistent radical-anion of the ketone. This radical-radical coupling negates unfavourable steric interactions of ionic pathways and avoids the unstable alkoxy-radical of previous radical olefin-carbonyl couplings which were limited, as a result, to aldehydes. Applications of this novel and straightforward approach include the efficient synthesis of drug-molecules, key-intermediates in drug synthesis and site-selective late-stage-functionalisation.

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Section: Introductionmentioning

confidence: 99%

Dual-Catalysed Intermolecular Reductive Coupling of Dienes and Ketones

Mayerhofer,

Lippolis,

Teskey

2023

Preprint

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show abstract

“…A range of such reactivity has been investigated with aldehyde (or masked-aldehyde) coupling partners, initially by Mori [5] and Le Gendre and Moïse [6] before being extensively developed by the groups of Krische [7][8][9][10][11][12] and others [13,14] as a contemporary revolution of classical allylation chemistry. However, ketones remain challenging in all but a few limited cases (see below), [15] likely due to their lower electrophilicity and increased steric demands relative to aldehydes.…”

mentioning

confidence: 99%

Dual‐Catalysed Intermolecular Reductive Coupling of Dienes and Ketones**

Mayerhofer,

Lippolis,

Teskey

2023

Angew Chem Int Ed

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We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation of a cobalt hydride species and single‐electron‐reduction of ketones. Subsequent selective hydrogen‐atom‐transfer from the cobalt hydride generates an allylic radical which can selectively couple with the persistent radical‐anion of the ketone. This radical‐radical coupling negates unfavourable steric interactions of ionic pathways and avoids the unstable alkoxy‐radical of previous radical olefin‐carbonyl couplings which were limited, as a result, to aldehydes. Applications of this novel and straightforward approach include the efficient synthesis of drug‐molecules, key‐intermediates in drug synthesis and site‐selective late‐stage functionalisation.

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“…Eine Reihe solcher Reaktivitäten wurde mit Aldehyd-(oder maskierten AldehydÀ ) Kupplungspartnern untersucht, zunächst von Mori [5] und Le Gendre und Moïse, [6] bevor sie von den Gruppen von Krische [7][8][9][10][11][12] und anderen [13,14] als eine fortschrittliche Revolution der klassischen Allylierungschemie umfassend weiterentwickelt wurden. Ketone stellen jedoch bis auf wenige Ausnahmen (siehe unten) eine Herausforderung dar, [15] was wahrscheinlich auf ihre geringere Elektrophilie und die höheren sterischen Anforderungen im Vergleich zu Aldehyden zurückzuführen ist. Es wurden zwei bemerkenswerte Lösungen für dieses Problem entwickelt.…”

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Dual‐katalysierte intermolekulare reduktive Kopplung von Dienen und Ketonen**

Mayerhofer,

Lippolis,

Teskey

2023

Angewandte Chemie

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We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation of a cobalt hydride species and single‐electron‐reduction of ketones. Subsequent selective hydrogen‐atom‐transfer from the cobalt hydride generates an allylic radical which can selectively couple with the persistent radical‐anion of the ketone. This radical‐radical coupling negates unfavourable steric interactions of ionic pathways and avoids the unstable alkoxy‐radical of previous radical olefin‐carbonyl couplings which were limited, as a result, to aldehydes. Applications of this novel and straightforward approach include the efficient synthesis of drug‐molecules, key‐intermediates in drug synthesis and site‐selective late‐stage functionalisation.

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Direct use of 1,3-dienes for the allylation of ketones via catalytic hydroindation

Abstract: In this study, in situ catalytically generated allylic indium from 1,3 dienes and InCl2H was developed for use in the allylation of ketones.

Cited by 3 publications

References 46 publications

Dual-Catalysed Intermolecular Reductive Coupling of Dienes and Ketones

Dual-Catalysed Intermolecular Reductive Coupling of Dienes and Ketones

Dual‐Catalysed Intermolecular Reductive Coupling of Dienes and Ketones**

Dual‐katalysierte intermolekulare reduktive Kopplung von Dienen und Ketonen**

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