Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters **
Abstract: Herein we describe the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated α,β‐unsaturated esters, catalyzed by a bifunctional iminophosphorane (BIMP) superbase. The transformation provides the most direct access to pharmaceutically relevant enantioenriched γ‐nitroesters, utilizing feedstock chemicals, with unprecedented selectivity. The methodology exhibits a broad substrate scope, including β‐(fluoro) alkyl, aryl and heteroaryl substituted electrophiles, and was successfully applied on a gram scale with reduced catalyst loading, and, additionally, catalyst recovery was carried out. The formal synthesis of a range of drug molecules, and an enantioselective synthesis of (S)‐rolipram were achieved. Additionally, computational studies revealed key reaction intermediates and transition state structures, and provided rationale for high enantioselectivities, in good agreement with experimental results.
- Standort
-
Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
-
Online-Ressource
- Sprache
-
Englisch
- Erschienen in
-
Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters ** ; day:13 ; month:04 ; year:2023 ; extent:10
Angewandte Chemie ; (13.04.2023) (gesamt 10)
- Urheber
-
Rozsar, Daniel
Farley, Alistair J. M.
McLauchlan, Iain
Shennan, Benjamin D. A.
Yamazaki, Ken
Dixon, Darren
- DOI
-
10.1002/ange.202303391
- URN
-
urn:nbn:de:101:1-2023041315325940494966
- Rechteinformation
-
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
-
14.08.2025, 10:50 MESZ
Datenpartner
Dieses Objekt wird bereitgestellt von:
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- Rozsar, Daniel
- Farley, Alistair J. M.
- McLauchlan, Iain
- Shennan, Benjamin D. A.
- Yamazaki, Ken
- Dixon, Darren
Ähnliche Objekte (12)
Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters **
Copper-Catalyzed Enantioselective Reduction of α,β-Unsaturated Esters
Co (Salox)‐Catalyzed Enantioselective Reduction of α,β‐Unsaturated Esters
Enantioselective 1,4-Addition of Amides with α,β-Unsaturated Carbonyls
Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams
Chiral Cu(II)-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water
![Azaheterocycles based on α,β-unsaturated [alpha beta unsaturated] carbonyls](/assets/placeholder/searchResultMediaNoDigitisedMedia.png)
Azaheterocycles based on α,β-unsaturated [alpha beta unsaturated] carbonyls
Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands
Chromophore Activation of α,β‐Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions
Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters **
Copper-Catalyzed Enantioselective Reduction of α,β-Unsaturated Esters
Co (Salox)‐Catalyzed Enantioselective Reduction of α,β‐Unsaturated Esters
Enantioselective 1,4-Addition of Amides with α,β-Unsaturated Carbonyls
Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams
Chiral Cu(II)-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water
Azaheterocycles based on α,β-unsaturated [alpha beta unsaturated] carbonyls
Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands
Chromophore Activation of α,β‐Unsaturated Carbonyl Compounds and Its Application to Enantioselective Photochemical Reactions
Bifunctional Iminophosphorane‐Catalyzed Enantioselective Nitroalkane Addition to Unactivated α,β‐Unsaturated Esters **
Copper-Catalyzed Enantioselective Reduction of α,β-Unsaturated Esters
Co (Salox)‐Catalyzed Enantioselective Reduction of α,β‐Unsaturated Esters
Enantioselective 1,4-Addition of Amides with α,β-Unsaturated Carbonyls
Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Aryloxide‐Facilitated Catalyst Turnover in Enantioselective α,β‐Unsaturated Acyl Ammonium Catalysis
Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams
Chiral Cu(II)-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water
Azaheterocycles based on α,β-unsaturated [alpha beta unsaturated] carbonyls
Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands