Diastereoselective synthesis of half-sandwich chiral-at-metal cobaltacycles by oxidative cyclisation.

Chem Commun (Camb)

School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, UK.

Published: October 2012

Reaction of chiral ester linked diynes with chlorotris(triphenylphosphine)cobalt(I) and sodium cyclopentadienide gave (η(5)-cyclopentadienyl)(triphenylphosphine) cobaltacyclopentadiene complexes as single chiral-at-metal diastereoisomers, including a non-racemic example synthesised in three steps from (S)-3-butyn-2-ol.

Download full-text PDF

Source
http://dx.doi.org/10.1039/c2cc34837cDOI Listing

Publication Analysis

Top Keywords

diastereoselective synthesis
4
synthesis half-sandwich
4
half-sandwich chiral-at-metal
4
chiral-at-metal cobaltacycles
4
cobaltacycles oxidative
4
oxidative cyclisation
4
cyclisation reaction
4
reaction chiral
4
chiral ester
4
ester linked
4

Similar Publications

Organocatalytic, enantioselective decarboxylative Mannich reactions of α,β-unsaturated β'-ketoacids and isatin -Boc imines, to give the corresponding 3-carbamoyl-2-oxindole derivatives, were developed. Subsequent N-deprotection and diastereoselective, intramolecular, aza-Michael reaction of the free amine provides previously unreported spiro[indoline-3,2'-piperidine]-2,4'-diones.

View Article and Find Full Text PDF

Synthesis of Benzazepines Bearing Three Contiguous Carbon Stereocenters through Pd(II)-Catalyzed [3 + 2] Cycloaddition of -Aryl Nitrones with Allenoates.

J Org Chem

January 2025

State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin 541004, China.

A cascade reaction of Pd(II)/dppben-catalyzed [3 + 2] cycloaddition of -aryl nitrones with allenoates and sequential reduction has been developed for the synthesis of functionalized benzazepines bearing three contiguous carbon stereocenters in moderate to good yields ranging from 15 to 82% and high diastereoselectivity. The obtained benzazepines could be converted into various benzazepine scaffolds, and an estrone-derived benzazepine scaffold was prepared over four steps from estrone. More importantly, chiral benzazepine bearing three contiguous carbon stereocenters could be obtained in 88% ee value with chiral auxiliary.

View Article and Find Full Text PDF

The stereoselective synthesis of highly substituted cyclobutanes is essential for the development of lead candidates in drug discovery. Herein, we present a novel Rh(III)-catalyzed reaction pathway for synthesizing substituted cyclobutanes, which involves a concerted N-C bond formation and C-C bond cleavage between 2-aryl quinazolinones and alkylidenecyclopropanes. Notably, the combination of Rh(III) catalyst and HFIP solvent plays a critical role in facilitating the formation of cyclobutane rings.

View Article and Find Full Text PDF

A Stereoselective Oxidative Dimerization En Route to (-)-Lomaiviticin A.

Org Lett

January 2025

Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.

We describe a stereoselective synthesis of the dimeric diazofluorene , a potential precursor to the cytotoxic -symmetric bacterial metabolite (-)-lomaiviticin A (). An efficient route was developed to convert the tetracyclic diol to the diketone (five steps, 30% overall). Oxidative dimerization of the enoxysilane provided the -symmetric dimeric diazofluorene in 56% yield and with 15:1:0 diastereoselectivity.

View Article and Find Full Text PDF

The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!