Diastereodivergence in catalytic asymmetric conjugate addition of carbon nucleophiles DOI
Byungjun Kim,

Hooseung Lee,

In‐Sun Song

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

Catalytic asymmetric conjugate additions of carbon nucleophiles have emerged as a potent tool for constructing multi-stereogenic molecules with precise stereochemical control. This review explores the concept diastereodivergence in such reactions, focusing on strategies to achieve selective access diverse diastereomeric products upon carbon-carbon bond formation. Drawing from rich array examples, we delve into key approaches controlling outcome these transformations, including alteration alkene geometry, fine-tuning reaction parameters, synergistic catalysis, and isomerization adducts. Additionally, highlight iterative additions, showcasing their potential diastereodivergent synthesis methyl-branched stereocenters 1,3-relationships. By presenting concentrated overview this significant topic, aims provide valuable insights design execution stereodivergent catalytic offering new avenues advancing stereoselective structural diversity organic synthesis.

Language: Английский

Enantioselective Organocatalytic Conjugate Addition of Malonates to β,β-Disubstituted β-Trifluoromethyl Enones under High Pressure DOI Creative Commons
Alicja J. Połosak,

Michał P. Głowacki,

Piotr Kwiatkowski

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

The first enantioselective Michael addition of malonates to acyclic β,β-disubstituted enones has been developed. Sterically hindered β-trifluoromethyl α,β-unsaturated 2-acyl thiazoles and benzothiazoles were found be the most reactive groups in reaction catalyzed by bifunctional tertiary amine–thioureas (2–5 mol %). However, application hyperbaric conditions (8–10 kbar) was required. adducts containing quaternary stereogenic centers with a CF3 group obtained high yields (vs <1% at 1 bar) enantiomeric excesses up 95%.

Language: Английский

Citations

1
Enantioselective Conjugate Addition of Aldehydes to Oxetane- and Azetidine-Containing Nitroolefins: An Entry to Spirocyclic Pyrrolidines DOI
Alena Budinská, Quentin Lefebvre, Helma Wennemers

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Enantioselective amine-catalyzed conjugate additions of aldehydes to oxetane- and azetidine-containing nitroolefins afford γ-nitroaldehydes as key building blocks en route spirocyclic oxetane/azetidine-pyrrolidines. The study provided insights into the stability reactivity these β,β-disubstituted enabled enantioselective synthesis chiral oxetanes azetidines in moderate-to-high yields enantioselectivities. This approach expands synthetic access medicinally relevant scaffolds broadens scope organocatalytic transformations.

Language: Английский

Citations

0
Palladium‐Catalyzed Remote C–H Functionalization: Non‐Covalent Interactions and Reversibly Bound Templates DOI
Debabrata Maiti,

Amal Tom Sebastian,

Suman Maji

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 27, 2024

Abstract Pd‐catalysis has stood as a pivotal force in synthetic transformations for decades, maintaining its status paramount tool the realm of C−H bond activation. While functionalization at proximal positions become commonplace, achieving selective and sustainable access to distal continues captivate scientific endeavors. Recently, noteworthy trend emerged, focusing on utilization non‐covalent interactions address challenges associated with remote functionalization. The integration these into palladium catalysis stands justified response demands positions. This review delves latest advancements trends surrounding incorporation within field catalysis. Furthermore, it is emphasize that multifunctional templates, particularly those harnessing hydrogen bonding, present an elegant sophisticated approach activate bonds highly directed fashion. These templates showcase versatility demonstrate potential applications across diverse contexts area

Language: Английский

Citations

2
Reactions of Alkyl β‐Nitroacrylates with Arenes in Triflic Acid: Synthesis of Oximes of Alkyl 2,3‐Diaryl‐3‐oxopropanoates DOI

Yuliya V. Zhelonkina,

Olesya V. Khoroshilova, Alexander Yu. Ivanov

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(39)

Published: Oct. 18, 2023

Abstract Methyl or ethyl 3‐nitropropenoates (β‐nitroacrylates) AlkO(O)C 1 −C 2 H=C 3 H−NO in reaction with arenes ArH triflic acid CF SO H (TfOH) at room temperature h give rise to oximes of alkyl 2,3‐diaryl‐3‐oxopropanoates AlkO(O)C−CH(Ar)−C(Ar)=NOH yields 42–92 %. The obtained bearing ortho ‐methyl substituents the aryl ring exist as atropoisomers solutions. study protonated forms β‐nitroacrylates by NMR and DFT calculations has revealed that reactive electrophiles are species AlkO(HO + )C H−N (O)(OH) protosolvated on acceptor groups NO CO R. Plausible mechanism is based primary interaction aromatic nucleophiles these electrophilic onto their carbon C .

Language: Английский

Citations

3
Palladium‐Catalyzed Remote C–H Functionalization: Non‐Covalent Interactions and Reversibly Bound Templates DOI
Debabrata Maiti,

Amal Tom Sebastian,

Suman Maji

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 27, 2024

Abstract Pd‐catalysis has stood as a pivotal force in synthetic transformations for decades, maintaining its status paramount tool the realm of C−H bond activation. While functionalization at proximal positions become commonplace, achieving selective and sustainable access to distal continues captivate scientific endeavors. Recently, noteworthy trend emerged, focusing on utilization non‐covalent interactions address challenges associated with remote functionalization. The integration these into palladium catalysis stands justified response demands positions. This review delves latest advancements trends surrounding incorporation within field catalysis. Furthermore, it is emphasize that multifunctional templates, particularly those harnessing hydrogen bonding, present an elegant sophisticated approach activate bonds highly directed fashion. These templates showcase versatility demonstrate potential applications across diverse contexts area

Language: Английский

Citations

0
Enantioselective Michael Addition of 3-Hydroxy-2-pyridone to Nitroolefins using Cinchona-derived Bifunctional Organocatalysts DOI

Minseok Gi,

Daehyun Oh,

Sehun Yang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(34), P. 7017 - 7023

Published: Jan. 1, 2024

Despite the extensive use of N-heteroarenes in pharmaceuticals and natural products, efficient methods for selective alkylation at C-4 position 2-pyridone are scarce. We developed an enantioselective Michael addition 3-hydroxy-2-pyridone to nitroolefins using cinchona-derived bifunctional squaramide organocatalysts, achieving up 95% yield >99% ee. This selectivity is driven by organocatalysts' hydrogen bonding interactions with under mild conditions. method demonstrates reaction's versatility various nitroolefins, providing a sustainable approach synthesizing chiral high enantioselectivity regioselectivity environmentally friendly

Language: Английский

Citations

0
Diastereodivergence in catalytic asymmetric conjugate addition of carbon nucleophiles DOI
Byungjun Kim,

Hooseung Lee,

In‐Sun Song

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

Catalytic asymmetric conjugate additions of carbon nucleophiles have emerged as a potent tool for constructing multi-stereogenic molecules with precise stereochemical control. This review explores the concept diastereodivergence in such reactions, focusing on strategies to achieve selective access diverse diastereomeric products upon carbon-carbon bond formation. Drawing from rich array examples, we delve into key approaches controlling outcome these transformations, including alteration alkene geometry, fine-tuning reaction parameters, synergistic catalysis, and isomerization adducts. Additionally, highlight iterative additions, showcasing their potential diastereodivergent synthesis methyl-branched stereocenters 1,3-relationships. By presenting concentrated overview this significant topic, aims provide valuable insights design execution stereodivergent catalytic offering new avenues advancing stereoselective structural diversity organic synthesis.

Language: Английский

Citations

0