Noscapine Derivatives as New Chiral Catalysts in Asymmetric Synthesis­: Highly Enantioselective Addition of Diethylzinc to Aldehydes­

Mohebbi, Maryam; Bararjanian, Morteza; Ebrahimi, Samad Nejad; Smieško, Martin; Salehi, Peyman

doi:10.1055/s-0037-1609224

Cited by 9 publications

(2 citation statements)

References 7 publications

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“…Further data that support the findings of this study are available in the supplementary material of this article. Additional references cited within the Supporting Information [22–60] …”

Section: Supporting Informationmentioning

confidence: 99%

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

et al. 2023

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The Cu(OTf)2‐catalyzed alkyl–alkyl coupling reaction of a secondary substrate MeCH(OSO2Py)CH2CH2C6H4(4‐OMe) with a nBuLi‐based reagent prepared by transmetalation with MgBr2 ⋅ THF3 in THF produced a coupling product in 74 % yield. The use of soluble MgBr2 ⋅ THF3 in THF was required for this reaction. This method was applied to sBuLi and Ph(CH2)4Li. In contrast, transmetalation of MeLi with soluble MgCl2 ⋅ THF2 in THF produced the Me reagent, which was reactive for the coupling reaction. The reaction proceeded with inversion of the stereogenic carbon. Furthermore, (S)‐14‐methyloctadecan‐2‐one, a sex pheromone produced by lichen moths, was synthesized.

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“…Further data that support the findings of this study are available in the supplementary material of this article. Additional references cited within the Supporting Information [22–60] …”

Section: Supporting Informationmentioning

confidence: 99%

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

et al. 2023

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“…The aforementioned reactions performed in the presence of atropisomeric 1-phenylpyrroles 93 and 94 led to the opposite enantiomers of desired alcohol with high enantioselectivity (Scheme 34) [85]. Recent developments towards efficient, highly enantioselective addition of diethylzinc to aldehydes include the use of chiral derivatives such as (Figure 2): 5-cis-substituted proline derivatives (prolinols 95 and prolinamines 96) [86], proline-based N,N-dioxides 97 [87], pinane-based tridentate ligands 98 [88], axially chiral tridentate isoquinolinederived ligands 99 [89], chiral oxazoline-based systems 100 [90], thiophene-derived amino alcohols 101 [91], amino alcohols 102 [92], noscapine-derived β-amino alcohols 103 [93,94], chiral ferrocene and ruthenocene substituted aminomethylnaphthols 104 [95], and chiral P,N-ligands 105 [96]. Enantioselective aldol-type reaction of trifluorodiazomethane 109 with various aldehydes was efficiently catalyzed by quinine in the presence of diethylzinc in THF (Scheme 36) [98].…”

Section: Asymmetric Reactions In the Presence Of Zinc Ionsmentioning

confidence: 99%

Recent Advances in Selected Asymmetric Reactions Promoted by Chiral Catalysts: Cyclopropanations, Friedel–Crafts, Mannich, Michael and Other Zinc-Mediated Processes—An Update

2021

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The main purpose of this review article is to present selected asymmetric synthesis reactions in which chemical and stereochemical outcomes are dependent on the use of an appropriate chiral catalyst. Optically pure or enantiomerically enriched products of such transformations may find further applications in various fields. Among an extremely wide variety of asymmetric reactions catalyzed by chiral systems, we are interested in: asymmetric cyclopropanation, Friedel–Crafts reaction, Mannich and Michael reaction, and other stereoselective processes conducted in the presence of zinc ions. This paper describes the achievements of the above-mentioned asymmetric transformations in the last three years. The choice of reactions is related to the research that has been carried out in our laboratory for many years.

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Deciphering the mechanism behind efficient enantioselective ethylation with thiazolidine‐based amino alcohols

Tavares

Cacho

Costa

et al. 2021

Applied Organom Chemis

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Taking advantage of the opposite chirality of two privileged starting materials, l‐cysteine and d‐penicillamine, a wide range of thiazolidine‐based amino alcohols was synthesized. l‐Cysteine derivatives were more efficient chiral inductors than the d‐penicillamine ones, with ee up to 92% in the enantioselective ethylation of benzaldehyde. The scope of the best catalyst was evaluated using several aromatic, heteroaromatic, and aliphatic aldehydes, providing excellent (S)‐enantioselectivities. Given the opposite chirality of the l‐cysteine and d‐penicillamine thiazolidines, it was expected that the use of one or the other type of derivative as ligand would allow the formation of opposite configurations of the alkylated product. However, whereas the l‐cysteine thiazolidines predominantly gave the (S) form of the alkylated product, the d‐penicillamine ones led to both configurations. The significant difference in the stereochemical outcome of this reaction when catalyzed by the two types of ligands prompted us to investigate the reasons behind such results. Extensive quantum chemical calculations were performed in order to identify the transition state structures by which the enantioselective ethylation of benzaldehyde in the presence of these type of amino alcohols can proceed. An alternative path for the rate‐determining step was also explored and found decisive for the rationalization of the experimental outcomes. It was observed that the type of ligand dictates the accessible reaction paths for the formation of the chiral product, which ultimately determine the balance between the two possible configurations.

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Noscapine Derivatives as New Chiral Catalysts in Asymmetric Synthesis: Highly Enantioselective Addition of Diethylzinc to Aldehydes

Cited by 9 publications

References 7 publications

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

Recent Advances in Selected Asymmetric Reactions Promoted by Chiral Catalysts: Cyclopropanations, Friedel–Crafts, Mannich, Michael and Other Zinc-Mediated Processes—An Update

Deciphering the mechanism behind efficient enantioselective ethylation with thiazolidine‐based amino alcohols

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Noscapine Derivatives as New Chiral Catalysts in Asymmetric Synthesis­: Highly Enantioselective Addition of Diethylzinc to Aldehydes­

Cited by 9 publications

References 7 publications

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

Copper‐Catalyzed Coupling Reaction of Secondary Alkyl 2‐Pyridinesulfonates with Alkyl Lithium‐Based Reagents

Recent Advances in Selected Asymmetric Reactions Promoted by Chiral Catalysts: Cyclopropanations, Friedel–Crafts, Mannich, Michael and Other Zinc-Mediated Processes—An Update

Deciphering the mechanism behind efficient enantioselective ethylation with thiazolidine‐based amino alcohols

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Noscapine Derivatives as New Chiral Catalysts in Asymmetric Synthesis: Highly Enantioselective Addition of Diethylzinc to Aldehydes