Mechanistic Insights on the Stereoselective Nucleophilic 1,2-Addition to Sulfinyl Imines

Hennum, Martin; Fliegl, Heike; Gundersen, Lise‐Lotte; Eisenstein, Odile

doi:10.1021/jo402802j

Cited by 18 publications

(17 citation statements)

References 57 publications

(37 reference statements)

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“…The reaction of imine 16 (R=Ph) with MeMgBr has been analyzed by DFT calculations, concluding that the ( E )‐ 16 gives the corresponding intermediate 119 (Scheme 50). [69] The results, which are in agreement with the experimental data, were also extended to the same reaction with MeLi.…”

Section: Organomagnesium Compoundssupporting

confidence: 77%

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Foubelo

Yus

2020

The Chemical Record

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In this account the reactions of chiral N‐tert‐butylsulfinyl imines with organometallic reagents such as organoalkaline (lithium, sodium, potassium and cesium derivatives), organomagnesium, organozinc, organoboron, organoaluminium, organoindium and organosilicon compounds is comprehensively described. The reactivity in all cases is derived to synthetic applications in order to prepare interesting organic nitrogenated molecules, especially in the field of alkaloid compounds.

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Section: Organomagnesium Compoundssupporting

confidence: 77%

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Foubelo

Yus

2020

The Chemical Record

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“…A complete computational study was performed at the DFT level (B3LYP-6-31G (d,p) and cc-pVTZ optimization) by Eisenstein and co-workers on sulfinylaldimines. 11 They underlined the significant impact of the rapid equilibrium between E and Z isomers on imine reactivity and explained that good diastereoselectivities arise both from two crucial factors, the preference for the E isomer and the Lewis acidity of the metal; the outcome of this study could be easily extended to sulfinylketimines. In a more recent paper Foubelo, Buarque, and co-workers performed DFT calculations (B3LYP-d3bj/def2svp level) specifically for the addition reaction of 2-bromobenzylmagnesium bromide to tetralone-derived sulfinylketimine.…”

Section: Scheme 1 Diastereocontrolled 12-additions To Sulfinylketiminesmentioning

confidence: 85%

1,2-Additions on Chiral N-Sulfinylketimines: An Easy Access to Chiral α-Tertiary Amines

Carret¹,

Poisson²,

Berthiol³

et al. 2022

Synthesis

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Chiral α-tertiary amines, a motif present in α,α-disubstituted α-amino acids, in a wide range of natural products, and many drugs and drug candidates, are important targets in organic chemistry. Among the possible strategies, 1,2-addition to chiral N-sulfinylketimines is one of the best routes to form chiral α-tertiary amines with a high level of stereoselectivity. In this review, we focus first on the addition of organometallic reagents or other nucleophiles as enols or ylides to chiral N-sulfinylketimines. Then secondly we cover a selection of applications of these additions in the synthesis of valuable biologically active compounds.1 Introduction2 1,2-Addition Reaction Methodologies2.1 Organolithium Reagent Additions2.2 Grignard Additions2.3 Organozinc Reagent Additions2.4 Organoindium Reagent Additions2.5 Organoboron Reagent Additions2.6 Strecker Reactions2.7 Palladium-Catalyzed Reactions2.8 Enols, Enolates, and Other Deprotonated Reagent Additions2.9 Ylide Additions2.10 Heteroatom Nucleophiles2.11 Miscellaneous Reactions3 Applications to the Synthesis of Biologically Active Molecules4 Conclusions

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“…The topological analysis of ELF has recently demonstrated to be of great utility in analyzing C–C bond formation in a variety of non‐polar, polar and ionic organic reactions 37. The NCI analysis38 has also demonstrated their utility in the analysis of several reactions39 including nucleophilic additions to C=N bonds 40. We have carried out the complete ELF and NCI analyses for the IRCs corresponding to the most stable paths of the addition reactions of enolates ENa – c to nitrone NI (For animations showing movies of the reactions illustrating both ELF and NCI analyses see Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Mechanism Switch in Mannich‐Type Reactions: ELF and NCI Topological Analyses of the Reaction between Nitrones and Lithium Enolates

et al. 2015

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The mechanism of the addition of lithium enolates derived from esters, ketones and aldehydes to nitrones (Mannich‐type reaction) has been studied using DFT methods. While the reactions with α‐methoxy and α‐methyl enolates takes place through a stepwise mechanism, consisting of an initial nucleophilic attack of the enolate to the nitrone carbon followed by a second nucleophilic attack of the nitrone oxygen to the formed carbonyl group, the reaction with α‐unsusbtituted enolates takes place through a one‐step mechanism. The IRC analysis shows the presence of a hidden intermediate in agreement with one kinetic step two stages process. The topological analysis of the electronic localization function (ELF) confirms that only when the first C–C bond is formed, does the C–O bond formation begin. The NCI analyses, are also in agreement with the formation of intermediates for α‐methoxy and α‐methyl enolates and a highly asynchronous one‐step process in the case of α‐unsusbtituted enolates.

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Mechanistic Insights on the Stereoselective Nucleophilic 1,2-Addition to Sulfinyl Imines

Cited by 18 publications

References 57 publications

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

Chiral N‐tert‐Butylsulfinyl Imines: New Discoveries

1,2-Additions on Chiral N-Sulfinylketimines: An Easy Access to Chiral α-Tertiary Amines

Mechanism Switch in Mannich‐Type Reactions: ELF and NCI Topological Analyses of the Reaction between Nitrones and Lithium Enolates

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