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The first diastereoselective synthesis of (-)-1--lentiginosine from a common chiral -epoxyamide derived from 2-pyridincarbaldehyde is reported. This methodology involves a sequential oxirane ring opening and intramolecular 5-- cyclization of tosylate -epoxyalcohol to afford a diastereomeric mixture of indolizinium salts in a one-pot fashion, followed by regio- and diastereospecific pyridinium ring reduction.
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http://dx.doi.org/10.3390/molecules28093719 | DOI Listing |
Molecules
April 2023
Centro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Edif. IC9 Complejo de Ciencias, C.U., Puebla 72570, Mexico.
The first diastereoselective synthesis of (-)-1--lentiginosine from a common chiral -epoxyamide derived from 2-pyridincarbaldehyde is reported. This methodology involves a sequential oxirane ring opening and intramolecular 5-- cyclization of tosylate -epoxyalcohol to afford a diastereomeric mixture of indolizinium salts in a one-pot fashion, followed by regio- and diastereospecific pyridinium ring reduction.
View Article and Find Full Text PDFJ Org Chem
November 2022
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences, 70 Profsoyuznaya Street, 117393 Moscow, Russia.
The reaction of cyclopropenones with pyridines, having an attached integer-charged electron-withdrawing group (pyridinium, imidazolium, and phosphonium) was discovered to afford novel indolizin-1-ol derivatives in high yields with no chromatographic purification required. While being stable as solids, these indolizin-1-ols have a limited lifetime in solution. The study of reasons for such instability uncovered an aerobic oxidative pathway, eventually resulting in indolizine-1,7-dione dimers.
View Article and Find Full Text PDFChemistry
October 2019
LCC-CNRS, Université de Toulouse, CNRS, Toulouse, 31077, France.
Coupling between 5-bromoimidazo[1,5-a]pyridinium salts and malonate or arylacetate esters leads to a facile and straightforward access to the new mesoionic, fused, tricyclic system of imidazo[2,1,5-cd]indolizinium-3-olate. Mechanistic studies show that the reaction pathway consists of nucleophilic aromatic substitution on the cationic, bicyclic heterocycle by an enolate-type moiety and in the nucleophilic attack of a transient free N-heterocyclic carbene (NHC) species on the ester group; the relative order of these two steps depends on the nature of the starting ester. This work highlights the valuable implementation of free NHC species as key intermediates in synthetic chemistry, beyond their classical use as stabilizing ligands or organocatalysts.
View Article and Find Full Text PDFChem Commun (Camb)
February 2017
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Various substituted indolizidinium, quinolizinium and pyrido[1,2-a]azepinium salts synthesized from benzaldehydes (or α,β-unsaturated aldehydes) and alkyne-amines catalyzed by rhodium complexes via C-H activation are demonstrated. The reaction was carried out under mild reaction conditions using Cu(BF)·6HO as oxidant and anion source and inexpensive oxygen as a co-oxidant. A reaction mechanism involving imine formation followed by an ortho C-H activation, alkyne insertion and reductive elimination via a 7-membered rhodacycle is proposed.
View Article and Find Full Text PDFInorg Chem
August 2015
Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, UMR 6521, CNRS-Université de Bretagne Occidentale, 6 Avenue Victor Le Gorgeu CS 93837, F-29238 Brest cedex 3, France.
The new BPMPB ligand, namely, bis[1-bis(2-pyridylmethyl),1 (pyridyl)]butyne, can be very easily obtained as a side product in the known reaction of picolyl chloride and sodium acetylide (which major product is the known terminal alkyne-substituted tripod). This symmetrical ligand contains two identical coordination sites with two methylenepyridines and one pyridyl group on each side, linked by an alkyne function providing a semirigid segment. Together with the molecular structure of the ligand which is reported, we describe the preparation of complexes with Fe(II)Cl2, Co(II)Cl2, Ni(II)Cl2, Cu(I)Cl, and Zn(II)Cl2 salts.
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