Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Development of an enantioselective route toward the Lycopodium alkaloids: total synthesis of lycopodine.

ABSTRACT: Synthesis of a C(15)-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitates enantioselective, intramolecular Michael additions. A detailed mechanistic discussion is provided for both the intramolecular Michael addition and the sulfone rearrangement. Finally, the application of these discoveries to the enantioselective total synthesis of alkaloid lycopodine is described.

SUBMITTER: Yang H

PROVIDER: S-EPMC2943527 | biostudies-literature | 2010 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Development of an enantioselective route toward the Lycopodium alkaloids: total synthesis of lycopodine.

Yang Hua H Carter Rich G RG

The Journal of organic chemistry 20100801 15

Synthesis of a C(15)-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitates enantioselective, intramolecular Michael add ...[more]

PMID: 20586477

Similar Datasets

Methoxypyridines in the synthesis of Lycopodium alkaloids: total synthesis of (+/-)-lycoposerramine R.

Project description:A methoxypyridine serves as a masked pyridone in a concise synthesis of the Lycopodium alkaloid lycoposerramine R, which has been prepared for the first time. The key step of the synthesis is the use of an Eschenmoser Claisen rearrangement to forge a key quaternary carbon center.

| S-EPMC2878394 | biostudies-literature

Synthetic studies on pseudo-dimeric Lycopodium alkaloids: total synthesis of complanadine B.

Project description: Not available

| S-EPMC3829996 | biostudies-literature

Enantioselective total synthesis of tricyclic myrmicarin alkaloids.

Project description:[reaction: see text] An enantioselective gram-scale synthesis of a key dihydroindolizine intermediate for the preparation of myrmicarin alkaloids is described. Key transformations in this convergent approach include a stereospecific palladium-catalyzed N-vinylation of a pyrrole with a vinyl triflate, a copper-catalyzed enantioselective conjugate reduction of a beta-pyrrolyl enoate, and a regioselective Friedel-Crafts reaction. The synthesis of optically active and isomerically pure samples of (4aR)-myrmicarins 215A, 215B, and 217 in addition to their respective C4a-epimers is presented.

| S-EPMC2992882 | biostudies-literature

New Lycopodium alkaloids from Lycopodium obscurum

Project description:Three new Lycopodium alkaloids, obscurumines C-E (1–3), along with nine known compounds, were isolated from the club moss Lycopodium obscurum L. Structures of the new compounds were determined on the basis of their spectroscopic analysis and the relative configurations of 1 were established by X-ray crystallographic analysis. All the new isolates were tested for the acetylcholinesterase (AChE) inhibitory activity. Electronic Supplementary Material Supplementary material is available for this article at 10.1007/s13659-013-0015-x and is accessible for authorized users.

| S-EPMC4131663 | biostudies-literature

Stereocontrolled enantioselective total synthesis of the [2+2] quadrigemine alkaloids.

Project description:A unified strategy for enantioselective total synthesis of all stereoisomers of the 2+2 family of quadrigemine alkaloids is reported. In this approach, two enantioselective intramolecular Heck reactions are carried out at the same time on precursors fashioned in four steps from either meso- or (+)-chimonanthine to form the two critical quaternary carbons of the peripheral cyclotryptamine rings of these products. Useful levels of catalyst control are realized in either desymmetrizing a meso precursor or controlling diastereoselectivity in elaborating C2-symmetic intermediates. None of the synthetic quadrigemines are identical with alkaloids isolated previously and referred to as quadrigemines A and E. In addition, we report improvements in our previous total syntheses of (+)- or (-)-quadrigemine C that shortened the synthetic sequence to 10 steps and provided these products in 2.2% overall yield from tryptamine.

| S-EPMC4526107 | biostudies-literature

Concise and enantioselective total synthesis of (-)-mehranine, (-)-methylenebismehranine, and related Aspidosperma alkaloids.

Project description:We report an efficient and highly stereoselective strategy for the synthesis of Aspidosperma alkaloids based on the transannular cyclization of a chiral lactam precursor. Three new stereocenters are formed in this key step with excellent diastereoselectivity due to the conformational bias of the cyclization precursor, leading to a versatile pentacyclic intermediate. A subsequent stereoselective epoxidation followed by a mild formamide reduction enabled the first total synthesis of the Aspidosperma alkaloids (-)-mehranine and (+)-(6S,7S)-dihydroxy-N-methylaspidospermidine. A late-stage dimerization of (-)-mehranine mediated by scandium trifluoromethanesulfonate completed the first total synthesis of (-)-methylenebismehranine.

| S-EPMC4240000 | biostudies-literature

Lycoplanines B-D, Three Lycopodium Alkaloids from Lycopodium complanatum.

Project description:A novel C17N Lycopodium alkaloid (LA), lycoplanine B (1), containing an unusual formyl group, along with two new LAs, lycoplanines C (2) and D (3), were isolated from the whole plant of Lycopodium complanatum. Their structures were elucidated by extensive NMR techniques, including 1D- and 2D-NMR experiments, as well as comparing their spectral data with those of the known analogues. A possible biogenetic pathway for 1 was also proposed.

| S-EPMC5971032 | biostudies-literature

Bioinspired Diversification Approach Toward the Total Synthesis of Lycodine-Type Alkaloids.

Project description:Nitrogen heterocycles (azacycles) are common structural motifs in numerous pharmaceuticals, agrochemicals, and natural products. Many powerful methods have been developed and continue to be advanced for the selective installation and modification of nitrogen heterocycles through C-H functionalization and C-C cleavage approaches, revealing new strategies for the synthesis of targets containing these structural entities. Here, we report the first total syntheses of the lycodine-type Lycopodium alkaloids casuarinine H, lycoplatyrine B, lycoplatyrine A, and lycopladine F as well as the total synthesis of 8,15-dihydrohuperzine A through bioinspired late-stage diversification of a readily accessible common precursor, N-desmethyl-β-obscurine. Key steps in the syntheses include oxidative C-C bond cleavage of a piperidine ring in the core structure of the obscurine intermediate and site-selective C-H borylation of a pyridine nucleus to enable cross-coupling reactions.

| S-EPMC8017526 | biostudies-literature

Total synthesis of the lycopodium alkaloid (+)-serratezomine A.

Project description:The first total synthesis of (+)-serratezomine A is described. Key aspects of the synthesis include (a) the first deployment of free-radical-mediated vinyl amination (an intramolecular alkyne aminostannation) in a complex target synthesis, (b) the use of a beta-stannyl enamine as the lynchpin for convergent assembly of the natural product backbone, (c) the use of an oxidative allylation promoted by cerium(IV) (CAN) to establish the all-carbon quaternary chiral center with the proper configuration, and (d) an intramolecular substitution reaction to form the sensitive bridging lactone. Overall, 15 steps (longest linear sequence) are required to prepare the natural product from a commercially available aldehyde, and assembly of the contiguous array of six stereocenters is accomplished with high stereocontrol.

| S-EPMC2677822 | biostudies-literature

Concise total syntheses of the Lycopodium alkaloids (+/-)-nankakurines A and B via luciduline.

Project description:Total syntheses of the Lycopodium alkaloids nankakurines A and B have been accomplished in 6 and 7 steps, respectively, via a sequence that passes through a third Lycopodium alkaloid, luciduline, and forgoes the use of protecting groups on nitrogen. Key features include a short preparation of luciduline followed by a concise and stereoselective aminoallylation/ring-closing metathesis protocol to fashion the spiropiperidine ring common to nankakurines A and B.

| S-EPMC2804776 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

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