Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A catalytic enantioselective tandem allylation strategy for rapid terpene construction: application to the synthesis of pumilaside aglycon.

ABSTRACT: Catalytic enantioselective 1,2-diboration of 1,3-dienes followed by cascade allylborations with dicarbonyls provides rapid entry into carbocyclic reaction products. The stereochemical course of this reaction was studied along with its application in the synthesis of pumilaside aglycon.

SUBMITTER: Ferris GE

PROVIDER: S-EPMC3625973 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A catalytic enantioselective tandem allylation strategy for rapid terpene construction: application to the synthesis of pumilaside aglycon.

Ferris Grace E GE Hong Kai K Roundtree Ian A IA Morken James P JP

Journal of the American Chemical Society 20130207 7

Catalytic enantioselective 1,2-diboration of 1,3-dienes followed by cascade allylborations with dicarbonyls provides rapid entry into carbocyclic reaction products. The stereochemical course of this reaction was studied along with its application in the synthesis of pumilaside aglycon. ...[more]

PMID: 23390951

Similar Datasets

Catalytic enantioselective conjugate allylation of unsaturated methylidene ketones.

Project description:The use of unsaturated methylidene ketones in catalytic conjugate allylations allows a significant expansion in substrate scope and, with appropriate chiral ligands, occurs in a highly enantioselective fashion.

| S-EPMC3065356 | biostudies-literature

Catalytic enantioselective one-pot aminoborylation of aldehydes: a strategy for construction of nonracemic ?-amino boronates.

Project description:We report a strategy for the conversion of aldehydes to enantiomerically enriched ?-amino boronates through the intermediacy of in situ-generated silylimines. This transformation is brought about by Pt-catalyzed asymmetric addition of B2(pin)2 across the imine double bond. An attractive feature of the intermediate diboration adduct is that it can be acylated directly and provides convenient access to important N-acyl ?-amino boronic ester derivatives.

| S-EPMC3752158 | biostudies-literature

Catalytic enantioselective allylation of dienals through the intermediacy of unsaturated pi-allyl complexes.

Project description:The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester [allylB(pin)] to alpha,beta,gamma,delta-unsaturated aldehydes is described. This reaction results in a remarkable inversion of substrate olefin geometry, providing the Z,E-configured reaction product in good enantioselectivity and olefin stereoselectivity. The reaction appears to proceed by conversion of the dienal to an unsaturated pi-allyl complex followed by reductive elimination via transition state II. Enantioselectivities range from 73-94% ee for a range of delta-substituted dienals when chiral ligand L3 is employed.

| S-EPMC2750882 | biostudies-other

11-Step enantioselective synthesis of (-)-lomaiviticin aglycon.

Project description:Lomaiviticins A and B are complex antitumor antibiotics that were isolated from a strain of Micromonospora. A confluence of several unusual structural features renders the lomaiviticins exceedingly challenging targets for chemical synthesis. We report an 11-step, enantioselective synthetic route to lomaiviticin aglycon. Our route proceeds by late-stage, stereoselective dimerization of two equivalent monomeric intermediates, a transformation that may share parallels with the natural products' biosyntheses. The route we describe is scalable and convergent, and it lays the foundation for determination of the mode of action of these natural products.

| S-EPMC5357143 | biostudies-literature

Successive Nucleophilic and Electrophilic Allylation for the Catalytic Enantioselective Synthesis of 2,4-Disubstituted Pyrrolidines.

Project description:Successive nucleophilic and electrophilic allylation mediated by the bis-Boc-carbonate derived from 2-methylene-1,3-propane diol enables formation of enantiomerically enriched 2,4-disubstituted pyrrolidines. An initial enantioselective iridium-catalyzed transfer hydrogenative carbonyl C-allylation is followed by Tsuji-Trost N-allylation using 2-nitrobenzenesulfonamide. Subsequent Mitsunobu cyclization provides the N-protected 2,4-disubstituted pyrrolidines.

| S-EPMC6475487 | biostudies-literature

Tandem sequential catalytic enantioselective synthesis of highly-functionalised tetrahydroindolizine derivatives.

Project description:An isothiourea-catalysed enantioselective synthesis of novel tetrahydroindolizine derivatives is reported through a one-pot tandem sequential process. The application of 2-(pyrrol-1-yl)acetic acid in combination with either a trifluoromethyl enone or an α-keto-β,γ-unsaturated ester in an enantioselective Michael addition-lactonisation process, followed by in situ ring-opening and cyclisation, led to a range of 24 tetrahydroindolizine derivatives containing three stereocentres in up to >95 : 5 dr and >99 : 1 er.

| S-EPMC8152628 | biostudies-literature

Catalytic enantioselective construction of axial chirality in 1,3-disubstituted allenes.

Project description:Metal-catalyzed enantioselective construction of the loosening axial allene chirality spreading over three carbon atoms using a chiral ligand is still a significant challenge. In the literature, steric effect of the substrates is the major strategy applied for such a purpose. Herein, we present a general palladium-catalyzed asymmetrization of readily available racemic 2,3-allenylic carbonates with different types of non-substituted and 2-substituted malonates using (R)-(-)-DTBM-SEGPHOS as the preferred ligand to afford 1,3-disubstituted chiral allenes with 90~96% ee. This protocol has been applied to the first enantioselective synthesis of natural product, (R)-traumatic lactone. Control experiments showed that in addition to the chiral ligand, conducting this transformation via Procedure C, which excludes the extensive prior coordination of the allene unit in the starting allene with Pd forming a species without the influence of the chiral ligand, is crucial for the observed high enantioselectivity.

| S-EPMC6355870 | biostudies-other

Enantioselective conjugate allylation of cyclic enones.

Project description:Enantioselective organocatalytic 1,2-allylation of a cyclic enone followed by anionic oxy-Cope rearrangement delivered the ketone as a mixture of diastereomers. This appears to be a general method for the net enantioselective conjugate allylation of cyclic enones.

| S-EPMC3237403 | biostudies-literature

A tandem dearomatization/rearomatization strategy: enantioselective N-heterocyclic carbene-catalyzed α-arylation.

Project description:In this study, the first example of the carbene-catalyzed tandem dearomatization/rearomatization reaction of azonaphthalenes with α-chloroaldehydes is described. This protocol enables the efficient assembly of chiral dihydrocinnolinone derivatives in good yields with excellent enantioselectivities (up to 99% ee). Moreover, this strategy enables not only the highly enantioselective NHC-catalyzed nucleophilic aromatic substitution, but also a formal Csp2-Csp3 bond formation.

| S-EPMC6385844 | biostudies-other

Catalytic enantioselective Cr-mediated propargylation: application to halichondrin synthesis.

Project description:A catalytic enantioselective propargylation in the presence of 10 mol % of Cr catalyst prepared from Cr(III) bromide and (R)-sulfonamide E furnishes homopropargyl alcohol 8 in 78% yield with 90% ee. Coupled with the workup based on Amano-lipase, this method provides a practical synthesis of optically pure 8 on a multigram scale. With maintenance of its optical purity, 8 has been converted to 1b, the C14-C19 building block of halichondrins and E7389, in two steps.

| S-EPMC2760007 | 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