AI Article Synopsis

  • - Acryloyl chlorides, aldehydes, and PhSLi can undergo a direct aldol cascade reaction using MgBr2 x OEt2 to create thioester enolates, leading to the formation of alpha-alkenyl-beta'-hydroxy thioesters through oxidative elimination.
  • - This method is quick, efficient, and broadly applicable, even for beta-substituted acryloyl chlorides.
  • - It offers a valuable alternative to the Morita-Baylis-Hillman reaction, expanding the range of synthetic possibilities available to chemists.

Article Abstract

Acryloyl chlorides, aldehydes, and PhSLi undergo a direct aldol cascade sequence in the presence of MgBr2 x OEt2 via in situ derived thioester enolates, which is followed by oxidative elimination to give alpha-alkenyl-beta'-hydroxy thioesters. Overall, the procedure is rapid, efficient, and generally applicable, even to beta-substituted acryloyl chlorides, thus providing an alternative to the Morita-Baylis-Hillman reaction with substantially greater synthetic scope and utility.

Download full-text PDF

Source
http://dx.doi.org/10.1021/ol801896qDOI Listing

Publication Analysis

Top Keywords

morita-baylis-hillman reaction
8
alpha-alkenyl-beta'-hydroxy thioesters
8
acryloyl chlorides
8
overcoming limitations
4
limitations morita-baylis-hillman
4
reaction rapid
4
rapid general
4
general synthesis
4
synthesis alpha-alkenyl-beta'-hydroxy
4
thioesters acryloyl
4

Similar Publications

Recent advances in the reactions of isatin-derived MBH carbonates for the synthesis of spirooxindoles.

Org Biomol Chem

January 2025

Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin 300384, P. R. China.

As one of the main fragments in medical drugs, spirooxindole has received considerable attention from organic and medicinal chemists. In the past few decades, chemists have been searching for more straightforward and efficient methods to produce compounds containing a spirooxindole fragment. In this regard, isatin-derived Morita-Baylis-Hillman (MBH) carbonates have been widely used as versatile building blocks for the synthesis of spirooxindole structures.

View Article and Find Full Text PDF

Pd/Cu Catalyzed Asymmetric Allylation for Stereodivergent Synthesis of Glutamic Acid Derivatives.

Chemistry

December 2024

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.

A synergistic Pd/Cu catalyst system has been developed for stereodivergent transformation of Morita-Baylis-Hillman (MBH) carbonates and Schiff bases derived from simple amino acids to afford a series of optically active β-branched γ-methyleneglutamic acid derivatives with adjacent tertiary/tertiary and quaternary/tertiary stereocenters in high yields (up to 96 %) with excellent diastereo- and enantioselectivities (>20/1 dr and >99 % ee in most cases) under mild conditions. The use of SKP ligand is disclosed to be crucial for the success of the transformation, and in particular allowing the reaction to proceed at low catalyst loading (0.02 mol % for Pd and 0.

View Article and Find Full Text PDF

An unexpected phosphine-catalyzed controllable three-component domino reaction involving [1 + 2 + 2] annulation and [1 + 2 + 2]/[3 + 2] sequential annulation reaction of 2-arylmethylidene cyanoacetates/malononitriles with Morita-Baylis-Hillman (MBH) carbonates has been developed. A broad range of densely functionalized cyclopentanes and diquinanes bearing five or four consecutive stereogenic centers, including two all-carbon quaternary stereocenters, were smoothly acquired in moderate to excellent yields under mild reaction conditions from readily available materials. Moreover, this divergent transformation enables the simultaneous generation of three or four new C-C bonds and one or two carbocyclic rings in only one step.

View Article and Find Full Text PDF

Organocatalytic Stereodivergent Dearomatization and -Acylation of 2-Amino-3-subsituted Indoles.

Org Lett

December 2024

Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, College of Science, Southern University of Science and Technology Guangming Advanced Research Institute, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China.

Organocatalytic chemo- and enantioselective reactions of 2-amino-3-subsituted indoles have been achieved for the first time. Via asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates, organocatalytic enantioselective dearomatization of 2-amino-3-subsituted indoles afforded an array of enantioenriched 3,3-disubstituted indolin-2-imines bearing a quaternary carbon stereocenter in 34-79% yields with 61-91% ee. With BocO as reaction partner, the organocatalytic enantioselective -acylation of 2-amino-3-subsituted indoles was established to furnish C-N axially chiral products in 22-98% yields with 73-92% ee.

View Article and Find Full Text PDF

Visible light-promoted α-aminoalkyl radical-triggered α-aminoalkylation and α-diaminoalkylation of Morita-Baylis-Hillman acetates with -methyl arylamines to synthesize -containing alkyl acrylates and γ,γ-diaminobutyl esters was reported. Photoinduced α-aminoalkylation is carried out with Na-eosin Y as an organophotocatalyst at room temperature under metal- and oxidant-free conditions. In particular, the α-diaminoalkylation is performed via α-aminoalkyl radical addition/elimination followed by a catalyst-controlled selective α-aminoalkyl radical addition strategy in one step under the [Ir(dtbbpy)(bpy))]PF/KF catalytic system.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!