Asymmetric Vinylogous Mukaiyama‐Mannich Reactions of Heterocyclic Siloxy Dienes with Ellman's Fluorinated Aldimines

Fustero, Santos; Rodenes, Miriam; Román, Raquel; Sedgwick, Daniel; Aguado, J.; Soloshonok, Vadim A.; Han, Jianlin; Mei, Haibo; Medio‐Simón, Mercedes; Barrio, Pablo

doi:10.1002/adsc.201900464

Cited by 7 publications

(3 citation statements)

References 49 publications

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“…[60] One year later, we described a simple strategy for the preparation of chiral γ-monosubstituted and γ,γ-disubstituted butenolides 61 and butyrolactams 62 by reaction of heterocyclic silyloxy dienes 63 and fluorinated Ellman's aldimines 56 through a process that implies an asymmetric vinylogous Mukaiyama-Mannich-type reaction (VMMnR) as the key step. [62] Although this kind of processes had been quite well studied in the case of non-fluorinated aldimines, [63] only a few examples of the use of fluorinated aldimines in VMMnR had been described for the asymmetric preparation of the corresponding fluorinated butenolides.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Fluorinated Imines in Tandem and Cycloaddition Reactions

Escorihuela

Fustero

2023

The Chemical Record

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The chemistry of fluorinated compounds has experienced extraordinary growth in recent decades due to the many and varied properties which many of the compounds that contain fluorinated groups possess. Among all of them, fluorinated chiral imines, in particular the Ellman's imines, are of great importance since they are some of the most interesting building blocks for the synthesis of a large number of enantioenriched carbocycles and heterocycles with extraordinary biological and synthetic properties. This personal account covers the most significant results obtained in our research group in the last two decades concerning asymmetric tandem reactions, paying special attention to the intramolecular aza‐Michael reaction (IMAMR), diversity oriented synthesis (DOS), asymmetric tandem reactions involving a p‐tolylsulfinyl group as chiral inducer and cycloaddition processes, in particular, the Pauson‐Khand reaction, [2+2+2]‐cycloadditions and metathesis reactions, starting mainly from enyne compounds and through the use of fluorinated chiral N‐sulfinyl imines and their derivatives as starting materials.

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Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Fluorinated Imines in Tandem and Cycloaddition Reactions

Escorihuela

Fustero

2023

The Chemical Record

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“…8 Alternatively, the 2-silyloxyfurans are explored as cyclic dienolate precursors in VMR to obtain enantioenriched butenolide motifs (Scheme 1c). 9 However, a plethora of reports are substantially limited to the addition of cyclic dienolates to acyclic aldimine or ketimine electrophiles. Despite vast advances made in the field, the developments in the enantioselective conjunction of two different heterocycles that could potentially provide quaternary stereogenic centers remain significant impediments.…”

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confidence: 99%

Chiral Spirophosphoric-Acid-Catalyzed Divergent Vinylogous Mannich and aza-Friedel–Crafts Reactions of 2-Methoxyfuran

Chao,

Jamwal,

Ananda Rao

et al. 2024

Org. Lett.

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The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γbutenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel−Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.

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“…1e) [41][42][43][44] . In this respect, the syntheses of homo-and heterofunctionalized, α-trifluoromethyl vicinal diamines [45][46][47][48][49][50][51][52] and other substituted trifluoropropylamines [52][53][54][55] are demanding.…”

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confidence: 99%

Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines

et al. 2020

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Regioselective vicinal diamination of carbon–carbon double bonds with two different amines is a synthetic challenge under transition metal-free conditions, especially for the synthesis of trifluoromethylated amines. However, the synthesis of ethylene diamines and fluorinated amine compounds is demanded, especially in the pharmaceutical sector. Herein, we demonstrate that the controllable double nucleophilic functionalization of an activated alkene synthon, originated from a trifluoropropenyliodonium salt with two distinct nucleophiles, enables the selective synthesis of trifluoromethylated ethylene amines and diamines on broad scale with high efficiency under mild reaction conditions. Considering the chemical nature of the reactants, our synthetic approach brings forth an efficient methodology and provides versatile access to highly fluorinated amines.

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Asymmetric Vinylogous Mukaiyama‐Mannich Reactions of Heterocyclic Siloxy Dienes with Ellman's Fluorinated Aldimines

Cited by 7 publications

References 49 publications

Fluorinated Imines in Tandem and Cycloaddition Reactions

Fluorinated Imines in Tandem and Cycloaddition Reactions

Chiral Spirophosphoric-Acid-Catalyzed Divergent Vinylogous Mannich and aza-Friedel–Crafts Reactions of 2-Methoxyfuran

Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines

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