Diarylprolinol with Trifluoromethyl Substituents and Diphenylprolinol‐Derived Perfluoroalkanesulfonamide as Organocatalysts in the Cross‐Aldol Reaction of Aldehydes

Hayashi, Yujiro; Tomikawa, Masashi; Mori, Naoki

doi:10.1002/adsc.202200266

Cited by 5 publications

(6 citation statements)

References 51 publications

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“…While asymmetric cross-aldol reaction was well studied in Maruoka's group, this useful process was also reported by Hayashi's [30] and Ikemoto's [31] group respectively. Diphenylprolinol-derived sulfonamide catalyst 13, which was the analogues of Jørgensen-Hayashi catalyst [32] , was tested in both researches (Scheme 8).…”

Section: Aldehydementioning

confidence: 77%

Bifunctional Sulfonamide as Hydrogen Bonding Catalyst in Catalytic Asymmetric Reactions: Concept and Application in the Past Decade

Zhu

Jiang

et al. 2022

Eur J Org Chem

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Since the first report of bifunctional sulfonamide organocatalysts in 2004, these chiral compounds have proven to be a reliable hydrogen-bonding catalyst and have been wildly employed in asymmetric organocatalysis due to its strong acidity and self-aggregation-free property. Herein, we review the application of bifunctional sulfonamide as hydrogenbonding catalyst after 2011, and our highlights will cover asymmetric process including aldol reaction, Michael addition, Mannich reaction, desymmetrization and cyclization.

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Section: Aldehydementioning

confidence: 77%

Bifunctional Sulfonamide as Hydrogen Bonding Catalyst in Catalytic Asymmetric Reactions: Concept and Application in the Past Decade

Zhu

Jiang

et al. 2022

Eur J Org Chem

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“…However, in the reactions of dichloroacetaldehyde, chloral, and ethyl glyoxylate, superior results and excellent enantioselectivities were obtained when catalyst 7 was employed. [75] These results are explained as follows. In the case of diarylprolinol 1, 1 reacts with an aldehyde to generate an enamine, which reacts with an electrophilic aldehyde.…”

Section: Diarylprolinol and Diphenylprolinol-derived Perfluoro-alkane...mentioning

confidence: 98%

“…Regarding the reactions of chloroacetaldehyde and 3‐triethylsilyl‐2‐propynal, catalyst 1 gave better results than did catalyst 7 . However, in the reactions of dichloroacetaldehyde, chloral, and ethyl glyoxylate, superior results and excellent enantioselectivities were obtained when catalyst 7 was employed [75] …”

Section: Diarylprolinol and Diphenylprolinol‐derived Perfluoro‐alkane...mentioning

confidence: 99%

Diarylprolinol as an Effective Organocatalyst in Asymmetric Cross‐Aldol Reactions of Two Different Aldehydes

Hayashi

2022

The Chemical Record

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The aldol reaction is one of the most important carbon‐carbon bond‐forming reactions in organic chemistry. Asymmetric direct cross‐aldol reaction of two different aldehydes has been regarded as a difficult reaction because of the side reactions such as self‐aldol reaction and over reaction. We found that trifluoromethyl‐substituted diarylprolinol, α,α‐bis[3,5‐bis(trifluoromethyl)phenyl]‐2‐pyrrolidinemethanol (1), is an effective organocatalyst that promotes several cross‐aldol reactions of aldehydes with excellent diastereo‐ and enantioselectivities. Acetaldehyde can be employed as a suitable nucleophilic aldehyde. Successful electrophilic aldehydes are ethyl glyoxylate, chloroacetaldehyde, dichloroacetaldehyde, chloral, α‐alkyl‐α‐oxo aldehyde, trifluoroacetaldehyde, glyoxal, alkenyl aldehyde, alkynyl aldehyde, and formaldehyde. Some of the aldehydes are commercially available as a polymer solution, an aqueous solution, or in the hydrated form. They can be used directly in the asymmetric aldol reaction as a commercially available form, which is a synthetic advantage. Given that the obtained aldol products possess several functional groups along with a formyl moiety, they are synthetically useful chiral building blocks.

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“…Hayashi and co‐workers [93] compared the reactivity, diastereoselectivity, and enantioselectivity of their diarylprolinol catalyst 54 with Ikemoto's diarylprolinol based amino perfluoroalkanesulfonamide catalyst 92 in the enantioselective cross‐aldol reactions. Propanal and acetaldehyde were chosen as donor aldehydes while a large number of aldehydes viz.…”

Section: Catalytic Enantioselective Cross‐aldol Reaction Of Unmodifie...mentioning

confidence: 99%

Efficient Catalytic Methods for Asymmetric Cross‐Aldol Reaction of Aldehydes

Ghosh

2024

ChemistrySelect

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The aldol reaction is one of the oldest and important C−C bond‐forming reactions between two carbonyl compounds where one carbonyl compound with a α‐hydrogen acts as a nucleophile (donor) and the second carbonyl compound acts as an electrophile (acceptor) leading to a β‐hydroxycarbonyl compound. Out of various possibilities with carbonyl compounds as donors and acceptors, the direct cross‐aldol reaction of two aldehydes is problematic because of several issues. Undesired side reactions such as donor acceptor pair reversal, self‐aldol reaction of the partner aldehyde(s) having α‐hydrogen atom(s), overreaction by further aldolization of the product β‐hydroxyaldehyde, aldol condensation followed by Michael‐type additions, and Tischenko‐type reactions are the other challenging issues. Generation of up to two stereogenic centres is common during the C−C bond formation. Hence, diastereoselectivity and enantioselectivity are additional concerns. To resolve the said problems, two approaches are in practice involving an unmodified aldehyde as acceptor (electrophile) and either an unmodified aldehyde or an aldehyde modified to its ene‐form (enolate/enamine) as the donor (nucleophile). This review highlights the selected methods for efficient asymmetric cross‐aldol reactions of aldehydes mediated by organocatalysts.

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Diarylprolinol with Trifluoromethyl Substituents and Diphenylprolinol‐Derived Perfluoroalkanesulfonamide as Organocatalysts in the Cross‐Aldol Reaction of Aldehydes

Cited by 5 publications

References 51 publications

Bifunctional Sulfonamide as Hydrogen Bonding Catalyst in Catalytic Asymmetric Reactions: Concept and Application in the Past Decade

Bifunctional Sulfonamide as Hydrogen Bonding Catalyst in Catalytic Asymmetric Reactions: Concept and Application in the Past Decade

Diarylprolinol as an Effective Organocatalyst in Asymmetric Cross‐Aldol Reactions of Two Different Aldehydes

Efficient Catalytic Methods for Asymmetric Cross‐Aldol Reaction of Aldehydes

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