Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Regioselective hydroformylation of allylic alcohols.

ABSTRACT: A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of ?-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.

SUBMITTER: Lightburn TE

PROVIDER: S-EPMC3096926 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Regioselective hydroformylation of allylic alcohols.

Lightburn Thomas E TE De Paolis Omar A OA Cheng Ka H KH Tan Kian L KL

Organic letters 20110419 10

A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen. ...[more]

PMID: 21504208

Similar Datasets

Regioselective Single-Electron Tsuji-Trost Reaction of Allylic Alcohols: A Photoredox/Nickel Dual Catalytic Approach.

Project description:A radical-mediated functionalization of allyl alcohol derived partners with a variety of alkyl 1,4-dihydropyridines via photoredox/nickel dual catalysis is described. This transformation transpires with high linear and E-selectivity, avoiding the requirement of harsh conditions (e.g., strong base, elevated temperature). Additionally, using aryl sulfinate salts as radical precursors, allyl sulfones can also be obtained. Kinetic isotope effect experiments implicated oxidative addition of the nickel catalyst to the allylic electrophile as the turnover-limiting step, supporting previous computational studies.

| S-EPMC7091330 | biostudies-literature

Access to stereodefined (Z)-allylsilanes and (Z)-allylic alcohols via cobalt-catalyzed regioselective hydrosilylation of allenes.

Project description:Hydrosilylation of allenes is the addition of a hydrogen atom and a silyl group to a carbon-carbon double bond of an allene molecule and represents a straightforward and atom-economical approach to prepare synthetically versatile allylsilanes and vinylsilanes. However, this reaction generally produces six possible isomeric organosilanes, and the biggest challenge in developing this reaction is to control both regioselectivity and stereoselectivity. The majorities of the developed allene hydrosilylation reactions show high selectivity towards the production of vinylsilanes or branched allylsilanes. By employing a cobalt catalyst generated from readily available and bench-stable cobalt precursor and phosphine-based ligands, here we show that this reaction proceeds under mild conditions in a regioselective and stereoselective manner, and affords synthetically challenging, but valuable linear cis-allylsilanes with excellent stereoselectivity (generally cis to trans ratios: >98:2). This cobalt-catalyzed (Z)-selective allene hydrosilylation provides a general approach to access molecules containing stereodefined (Z)-alkene units.

| S-EPMC5741631 | biostudies-literature

Enantioselective dichlorination of allylic alcohols.

Project description:The development of an enantioselective allylic alcohol dichlorination catalyzed by dimeric cinchona alkaloid derivatives and employing aryl iododichlorides as chlorine sources is reported. Reaction optimization, exploration of the substrate scope, and a model for stereoinduction are presented.

| S-EPMC3107004 | biostudies-literature

Regioselective trans-Carboboration of Propargyl Alcohols.

Project description:Proper choice of the base allowed trans-diboration of propargyl alcohols with B2(pin)2 to evolve into an exquisitely regioselective procedure for net trans-carboboration. The method is modular as to the newly introduced carbon substituent (aryl, methyl, allyl, benzyl, alkynyl), which is invariably placed distal to the -OH group.

| S-EPMC6727597 | biostudies-literature

Regioselective molybdenum-catalyzed allylic substitution of tertiary allylic electrophiles: methodology development and applications.

Project description:The first molybdenum-catalyzed allylic sulfonylation of tertiary allylic electrophiles is described. The method employs a readily accessible catalyst (Mo(CO)6/2,2'-bipyridine, both are commercially available) and represents the first example of the use of a group 6 transition metal-catalyst for allylic sulfonylation of substituted tertiary allylic electrophiles to form carbon-sulfur bonds. This atom economic and operationally simple methodology is characterized by its relatively mild conditions, wide substrate scope, and excellent regioselectivity profile, thus unlocking a new platform to forge sulfone moieties, even in the context of late-stage functionalization and providing ample opportunities for further derivatization through traditional Suzuki cross-coupling reactions.

| S-EPMC8159339 | biostudies-literature

Catalytic Asymmetric Synthesis of Branched Chiral Allylic Phenyl Ethers from (E)-Allylic Alcohols.

Project description:The first di-?-amidate dipalladium complexes and a new di-?-carboxylate dipalladium complex of the COP (cobalt oxazoline palladacycle) palladium(II) catalyst family are reported and characterized crystallographically. The di-?-amidate complex 3 or its enantiomer (ent-3) are the first asymmetric catalysts that allow commercially available, or readily accessible, (E)-2-alkene-1-ols to be transformed to enantioenriched branched allylic aryl ethers upon reaction of their trichloroacetimidate derivatives with phenols. The 3-aryloxy-1-alkene products are formed in high enantiomeric purity (typically 90-98% ee) and useful yields (61-88%).

| S-EPMC3689305 | biostudies-literature

Nickel-catalyzed enantioselective allylic alkylation of lactones and lactams with unactivated allylic alcohols.

Project description:The first nickel-catalyzed enantioselective allylic alkylation of lactone and lactam substrates to deliver products bearing an all-carbon quaternary stereocenter is reported. The reaction, which utilizes a commercially available chiral bisphosphine ligand, proceeds in good yield with a high level of enantioselectivity (up to 90% ee) on a range of unactivated allylic alcohols for both lactone and lactam nucleophiles. The utility of this method is further highlighted via a number of synthetically useful product transformations.

| S-EPMC5912103 | biostudies-other

Stereoselective cross-coupling between allylic alcohols and aldimines.

Project description:A cross-coupling reaction between an allylic alcohol and an imine is described for stereoselective allylation of aromatic and aliphatic imines. This method provides operationally simple, enantioselective access to functionalized homoallylic amines. Particularly noteworthy is direct use of a functionalized allylic alcohol as an allylating reagent without prederivatization, which obviates the use of preformed organometallic reagents or activated imine derivatives.

| S-EPMC2720054 | biostudies-literature

Catalytic asymmetric generation of (Z)-disubstituted allylic alcohols.

Project description:A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (-)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20-30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.

| S-EPMC2532596 | biostudies-literature

Catalytic Regio- and Enantioselective Haloazidation of Allylic Alcohols.

Project description:Herein we report a highly regio- and stereoselective haloazidation of allylic alcohols. This enantioselective reaction uses readily available materials and can be performed on a variety of alkyl-substituted alkenes and can incorporate either bromine or chlorine as the electrophilic halogen component. Both halide and azido groups of the resulting products can be transformed into valuable building blocks with complete stereospecificity. The first example of an enantioselective 1,4-haloazidation of a conjugated diene is reported as well as its application to a concise synthesis of an aza-sugar.

| S-EPMC6499076 | 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