Deacylative Allylation of Nitroalkanes: Unsymmetric Bisallylation by a Three‐Component Coupling

Grenning, Alexander J.; Tunge, Jon A.

doi:10.1002/anie.201006273

Cited by 57 publications

(23 citation statements)

References 52 publications

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“…While nitronate anions are known to undergo alkylation with alkyl radicals, these radicals are often accessed using highly undesirable methods such as stoichiometric alkylmetal reagents or highly complex alkylating agents [ 17 ]. Although allylation [ 18 – 23 ] and arylation [ 24 – 26 ] of nitroalkanes using palladium catalysis were known, prior to our work, no general catalytic methods for the alkylation of nitroalkanes existed.…”

Section: Resultsmentioning

confidence: 99%

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

Shimkin

Watson

2015

Beilstein J. Org. Chem.

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SummaryRecently, a number of papers have emerged demonstrating copper-catalyzed alkylation reactions of electron-rich small molecules. The processes are generally thought to be related to long established atom-transfer radical reactions. However, unlike classical reactions, these new transformations lead to simple alkylation products. This short review will highlight recent advances in alkylations of nitronate anions, alkenes and alkynes, as well as discuss current mechanistic understanding of these novel reactions.

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Section: Resultsmentioning

confidence: 99%

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

Shimkin

Watson

2015

Beilstein J. Org. Chem.

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“…One example of its utility, we have previously demonstrated DaA's ability to construct 1,6-dienes (cycloisomerization substrates 32-39 ) in a single pot via sequential palladium-catalysis. 18-19,40 …”

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confidence: 99%

Development of Asymmetric Deacylative Allylation

et al. 2013

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Herein we present the development of asymmetric deacylative allylation of ketone enolates. The reaction directly couples readily available ketone pronucleophiles with allylic alcohols using facile retro-Claisen cleavage to form reactive intermediates in situ. The simplicity and robustness of the reaction conditions is demonstrated by the preparation of > 6 grams of an allylated tetralone from commercially available materials. Furthermore, use of non-racemic PHOX ligands allows intermolecular formation of quaternary stereocenters directly from allylic alcohols.

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“…10 As shown herein, the DaA process maintains several hallmarks of decarboxylative allylation. Specifically, it A) allows the site-specific generation of carbanions via C–C cleavage, B) allows rapid synthesis of precursors via acetoacetic ester-like chemistries, and C) forms both nucleophilic and electrophilic reactive intermediates in situ .…”

Section: Introductionmentioning

confidence: 60%

“…Thus, our approach is unique since both the nucleophile and the electrophile are activated by a single C–C bond cleavage event. 10,12 In addition to facilitating intermolecular allylations, DaA is attractive since it results in alkylation of carbanions directly from allylic alcohols. 13 Herein, we wish to report our findings that many ketone pronucleophiles can undergo intermolecular deacylative allylation (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Deacylative Allylation: Allylic Alkylation via Retro-Claisen Activation

Grenning

Tunge

2011

J. Am. Chem. Soc.

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A new method for allylic alkylation of a variety of relatively non-stabilized carbon nucleophiles is described herein. In this process of “deacylative allylation” the coupling partners, an allylic alcohol and a ketone pronucleophile, undergo in situ retro-Claisen activation to generate an allylic acetate and a carbanion. In the presence of palladium, these reactive intermediates undergo catalytic coupling to form a new C–C bond. In comparision to unimolecular decarboxylative allylation, a commonly utilized method for allylation of carbon anions, deacylative allylation is an intermolecular process. Moreover, deacylative allylation allows the direct coupling of readily available allylic alcohols. Lastly, the full utility of deacylative allylation is demonstrated by the rapid construction of a variety 1,6-heptadienes via 3-component couplings.

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Deacylative Allylation of Nitroalkanes: Unsymmetric Bisallylation by a Three‐Component Coupling

Abstract: Use it and lose it! Allylic alcohols were used directly for the synthesis of diallylated nitroalkanes in a three‐component coupling based on the strategy of deacylative allylation for the in situ generation of a nucleophile and an allyl electrophile (see scheme).

Cited by 57 publications

References 52 publications

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

Development of Asymmetric Deacylative Allylation

Deacylative Allylation: Allylic Alkylation via Retro-Claisen Activation

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