Asymmetric Aldol Reaction of Dichloroacetaldehyde Catalyzed by Diarylprolinol

Hayashi, Yujiro; Nakamura, Daichi; Yasui, Yusuke; Iwasaki, Kotaro; Chiba, Hayato

doi:10.1002/adsc.201501111

Cited by 12 publications

(6 citation statements)

References 33 publications

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“…Hayashi et al . firstly reported dichloroacetaldehyde as an electrophilic aldehyde in an asymmetric aldol reaction with nucleophilic aldehydes catalyzed by diarylprolinol 1 b (Scheme ) …”

Section: Asymmetric Cross‐aldol Reactionsmentioning

confidence: 99%

“…Hayashi et al firstly reported dichloroacetaldehyde as an electrophilic aldehyde in an asymmetric aldol reaction with nucleophilic aldehydes catalyzed by diarylprolinol 1 b (Scheme 14). [26] Additional 3 equivalents of water proved to be beneficial in terms of conversion and diastereoselectivity. γ,γ-Dichloro-βhydroxyaldehydes 20 were used as transient intermediates to obtain the corresponding esters 21, isolated in good yields, good to excellent diastereoselectivity and high enantioselectivity.…”

Section: Asymmetric Cross-aldol Reactionsmentioning

confidence: 99%

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Diaryl Prolinols in Stereoselective Catalysis and Synthesis: An Update

2019

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Discovered more than one decade ago, α,α‐diaryl prolinols, most of them commercially available compounds, demonstrated to be distinctive organocatalysts in asymmetric synthesis. Their application successfully spanned across different carbon‐carbon or carbon‐heteroatom bond forming reactions and cascade processes, exploiting covalent and noncovalent activation of the reagents. In this minireview, the advances from 2013 up to the end of 2018 in α,α‐diaryl prolinols promoted stereoselective catalysis and synthesis of biologically active compounds, are illustrated.

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“…Hayashi et al . firstly reported dichloroacetaldehyde as an electrophilic aldehyde in an asymmetric aldol reaction with nucleophilic aldehydes catalyzed by diarylprolinol 1 b (Scheme ) …”

Section: Asymmetric Cross‐aldol Reactionsmentioning

confidence: 99%

Section: Asymmetric Cross-aldol Reactionsmentioning

confidence: 99%

Diaryl Prolinols in Stereoselective Catalysis and Synthesis: An Update

2019

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“…In the case of dichloroacetaldehyde, a commercially available hydrated form of dichloroacetaldehyde was employed [8m] . Catalyst 3 afforded a lower yield and diastereoselectivity than catalyst 1 under the same reaction conditions (entries 4 and 5).…”

Section: Figurementioning

confidence: 99%

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

2022

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The asymmetric cross-aldol reaction of two different aldehydes is a synthetically relevant reaction. Diarylprolinol catalyst with trifluoromethyl substituents and sulfonamide catalyst derived from diphenylprolinol are organocatalysts for the crossaldol reaction. The reactivity and stereoselectivity of these two catalysts were compared in the asymmetric cross-aldol reactions of propanal and acetaldehyde as nucleophilic aldehydes and several electrophilic aldehydes. Depending on the electrophilic aldehydes, the preferable catalyst differs. By the proper selection of these two catalysts, potentially synthetically useful chiral building blocks can be synthesized with diastereoselectivities of anti: syn = 2.6:1 ~> 20:1 and enantioselectivities of 60 > 98% ee.

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“…The reaction is general (Scheme 13). [38] The obtained products are synthetically useful: the βdichloro α-hydroxy moiety can be converted into alkyne or 1,1-dichloroalkene moieties under different reaction conditions with excellent enantioselectivity (Scheme 14).…”

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%

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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Asymmetric Aldol Reaction of Dichloroacetaldehyde Catalyzed by Diarylprolinol

Cited by 12 publications

References 33 publications

Diaryl Prolinols in Stereoselective Catalysis and Synthesis: An Update

Diaryl Prolinols in Stereoselective Catalysis and Synthesis: An Update

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

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

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