Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chiral multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita-Baylis-Hillman carbonates with maleimides.

ABSTRACT: We have developed a multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita-Baylis-Hillman (MBH) carbonates with maleimides, which can efficiently construct functionalized cyclopentenes bearing three contiguous stereocenters in moderate to excellent yields and excellent diastereo- and enantioselectivities. A plausible mechanism has been also proposed on the basis of control experiments and previous literature.

SUBMITTER: Deng HP

PROVIDER: S-EPMC3458726 | biostudies-literature | 2012

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chiral multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita-Baylis-Hillman carbonates with maleimides.

Deng Hong-Ping HP Wang De D Wei Yin Y Shi Min M

Beilstein journal of organic chemistry 20120716

We have developed a multifunctional thiourea-phosphine catalyzed asymmetric [3 + 2] annulation of Morita-Baylis-Hillman (MBH) carbonates with maleimides, which can efficiently construct functionalized cyclopentenes bearing three contiguous stereocenters in moderate to excellent yields and excellent diastereo- and enantioselectivities. A plausible mechanism has been also proposed on the basis of control experiments and previous literature. ...[more]

PMID: 23019436

Similar Datasets

Organocatalytic asymmetric allylic amination of Morita-Baylis-Hillman carbonates of isatins.

Project description:The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita-Baylis-Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee) and in high yields (up to 97%).

| S-EPMC3458744 | biostudies-literature

Asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates with ?-fluoro-?-keto esters.

Project description:In the presence of a commercially available Cinchona alkaloid as catalyst, the asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates, with ?-fluoro-?-keto esters as nucleophiles, have been successfully developed. A series of important fluorinated adducts, with chiral quaternary carbon centres containing a fluorine atom, was achieved in good yields (up to 93%), with good to excellent enantioselectivities (up to 96% ee) and moderate diastereoselectivities (up to 4:1 dr).

| S-EPMC3778419 | biostudies-literature

A facile and mild synthesis of trisubstituted allylic sulfones from Morita-Baylis-Hillman carbonates.

Project description:An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH) carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%-99%) with good to high selectivity (Z/E from 79:21 to >99:1). Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

| S-EPMC6272667 | biostudies-other

Morita-Baylis-Hillman reaction of acrylamide with isatin derivatives.

Project description:The Morita-Baylis-Hillman reaction of acrylamide, as an activated alkene, has seen little development due to its low reactivity. We have developed the reaction using isatin derivatives with acrylamide, DABCO as a promoter and phenol as an additive in acetonitrile. The corresponding aza version with acrylate and acrylonitrile has also been developed resulting in high product yields.

| S-EPMC4273229 | biostudies-literature

Application of 7-azaisatins in enantioselective Morita-Baylis-Hillman reaction.

Project description:7-Azaisatin and 7-azaoxindole skeletons are valuable building blocks in diverse biologically active substances. Here 7-azaisatins turned out to be more efficient electrophiles than the analogous isatins in the enantioselective Morita-Baylis-Hillman (MBH) reactions with maleimides using a bifunctional tertiary amine, ?-isocupreidine (?-ICD), as the catalyst. This route allows a convenient approach to access multifunctional 3-hydroxy-7-aza-2-oxindoles with high enantiopurity (up to 94% ee). Other types of activated alkenes, such as acrylates and acrolein, could also be efficiently utilized.

| S-EPMC4778495 | biostudies-literature

Expedient Organocatalytic Aza-Morita-Baylis-Hillman Reaction through Ball-Milling.

Project description:A ball-milling enabled tertiary amine catalyzed aza-Morita-Baylis-Hillman reaction is reported. The reaction process does not require solvent, has significantly shorter reaction times than previous methods and is reported on a range of imines and acrylate Michael acceptors across than 26 examples. A 12-fold scaled-up example is also reported as well as experimental comparisons to solution-based experiments and neat-stirred reactions.

| S-EPMC7885690 | biostudies-literature

Regio- and Stereoselective Electrochemical Alkylation of Morita-Baylis-Hillman Adducts.

Project description:Electrosynthesis is effectively employed in a general regio- and stereoselective alkylation of Morita-Baylis-Hillman compounds. The exposition of N-acyloxyphthalimides (redox-active esters) to galvanostatic electroreductive conditions, following the sacrificial-anode strategy, is proved an efficient and practical method to access densely functionalized cinnamate and oxindole derivatives. High yields (up to 80%) and wide functional group tolerance characterized the methodology. A tentative mechanistic sketch is proposed based on dedicated control experiments.

| S-EPMC9237826 | biostudies-literature

Dihydroquinolines, Dihydronaphthyridines and Quinolones by Domino Reactions of Morita-Baylis-Hillman Acetates.

Project description:An efficient synthetic route to highly substituted dihydroquinolines and dihydronaphthyridines has been developed using a domino reaction of Morita-Baylis-Hillman (MBH) acetates with primary aliphatic and aromatic amines in DMF at 50-90 °C. The MBH substrates incorporate a side chain acetate positioned adjacent to an acrylate or acrylonitrile aza-Michael acceptor as well as an aromatic ring activated toward SNAr ring closure. A control experiment established that the initial reaction was an SN2'-type displacement of the side chain acetate by the amine to generate the alkene product with the added nitrogen nucleophile positioned trans to the SNAr aromatic ring acceptor. Thus, equilibration of the initial alkene geometry is required prior to cyclization. A further double bond migration was observed for several reactions targeting dihydronaphthyridines from substrates with a side chain acrylonitrile moiety. MBH acetates incorporating a 2,5-difluorophenyl moiety were found to have dual reactivity in these annulations. In the absence of O2, the expected dihydroquinolines were formed, while in the presence of O2, quinolones were produced. All of the products were isolated in good to excellent yields (72-93%). Numerous cases (42) are reported, and mechanisms are discussed.

| S-EPMC7914960 | biostudies-literature

Asymmetric catalytic aza-Morita-Baylis-Hillman reaction for the synthesis of 3-substituted-3-aminooxindoles with chiral quaternary carbon centers.

Project description:The asymmetric catalytic aza-Morita-Baylis-Hillman (aza-MBH) reaction of isatin-derived ketimines with MVK has been established by using chiral amino and phosphino catalysts. The reaction resulted in biomedically important 3-substituted 3-amino-2-oxindoles in good yields (>80% for most cases) and with excellent enantioselectivity (90-99% ee). Twenty-eight cases assembled with chiral quaternary stereogenic centers have been examined under convenient systems.

| S-EPMC3590110 | biostudies-literature

Remarkable influence of microwave heating on Morita-baylis-Hillman reaction in PEG-200.

Project description:BackgroundMorita Baylis Hillman (MBH) reaction is used to introduce carbon-carbon or carbon-heteroatom bond in a molecule. The major drawback of this reaction is the relatively low product yield and long reaction time. Though notable changes have been made to improve the reaction rate and yield of MBH adduct by various groups, a reliable synthetic procedure under ambient temperature in presence moisture and air is remain unsolved. Continuing the effort to improve the rate and yield, we report here an eco-friendly and cost-effective method to generate MBH adducts. Non-volatile polyethylene glycol-200 is used as reusable solvents and the reaction was carried out under the influence of microwave energy.ResultsMicrowave irradiation have a remarkable influence on PEG suspended 4-Diazabicyclo [2.2.2] octane (DABCO) catalysed MBH reaction between aldehydes and ethyl acrylate. Molecular weight of the PEG is found to have a significant influence on the reaction yield. PEG-200 was the most efficient solvent and in combination with DABCO, the medium can be recycled upto three more runs. This reaction condition is successfully applied to obtain MBH adduct of five different aldehydes in very short time with excellent yield and the required catalyst concentration was very low compared to standard MBH reaction. Since the MBH adduct is an important reactive intermediates for many complex organic syntheses, this approach can be successfully utilised as an alternative to existing reaction conditions.ConclusionA new method was developed to improve the reaction rate and yield of MBH reaction The PEG 200-DABCO combination provides a sustainable, non-volatile, recyclable and environment friendly solvent medium to produce MBH adducts. This medium in combination with microwave energy proved to be very effective to introduce a new carbon-carbon or a carbon-heteroatom bond in a molecule.

| S-EPMC3483690 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data