Rosenthal's-reagent-mediated intramolecular cyclometallation of α,α-dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3-butadiene-embedded porphyrin(2.1.2.1), 6, which served as a reactive diene towards dienophiles such as dimethyl acetylenedicarboxylate (DMAD) and benzyne to give corresponding Diels-Alder adducts. Diels-Alder reaction of 6 and benzdiyne gave adducts 14, 15 a, and 15 b along with a trace amount of porphyrin(2.1.2.1) barrel 13. Stepwise routes using 14 or 15 a/15 b as a substrate allowed for the synthesis of 13 as a single stereoisomer. The nanobarrel structure for 13 was revealed by X-ray diffraction, where its cavity held two chloroform molecules via C-H⋅⋅⋅π interaction. DFT calculations revealed that the electrostatic attraction was dominant with binding energy of 32.8 kcal mol .
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202201327 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Low-Valent Zirconocene-Mediated Synthesis of Porphyrin(2.1.2.1)s and Its Extension to Synthesis of a Porphyrin(2.1.2.1) Nanobarrel.
Angew Chem Int Ed Engl
May 2022
Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, China.
Rosenthal's-reagent-mediated intramolecular cyclometallation of α,α-dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3-butadiene-embedded porphyrin(2.1.2.
View Article and Find Full Text PDFZirconocene-mediated intermolecular coupling of Si-tethered diynes with alkynes, ketones, aldehydes, and isocyanates by means of novel skeletal rearrangement of zirconacyclobutene-silacyclobutene and zirconacyclohexadiene-silacyclobutene fused-ring intermediates.
Chemistry
March 2005
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Bis(alkynyl)silanes react with low valent zirconocene species to afford zirconacyclobutene intermediates. These in situ generated reactive organometallic intermediates can react with alkynes, ketones, aldehydes, and isocyanates by means of a novel skeletal rearrangement. When a zirconacyclobutene intermediate was treated with an alkyne, an alpha-alkynylsilyl zirconacyclopentadiene was formed.
View Article and Find Full Text PDFZirconium sandwich complexes with eta(9) indenyl ligands: well-defined precursors for zirconocene-mediated coupling reactions.
J Am Chem Soc
December 2004
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA.
A family of isolable, well-defined bis-indenyl zirconium sandwich complexes, (eta(5)-C(9)H(5)-1,3-R(2))(eta(9)-C(9)H(5)-1,3-R(2))Zr (R = silyl, alkyl), have been prepared by either alkane reductive elimination or alkali metal reduction of a suitable zirconium(IV) dihalide precursor. Crystallographic characterization of two of these derivatives, R = SiMe(2)CMe(3) and CHMe(2), reveals unprecedented eta(9) coordination of one of the indenyl ligands. Variable-temperature and EXSY NMR studies establish that the eta(5) and eta(9) rings are rapidly interconverting in solution.
View Article and Find Full Text PDFZirconocene-mediated intermolecular coupling of one molecule of Si-tethered diyne with three molecules of organonitriles: one-pot formation of pyrrolo[3,2-c]pyridine derivatives via cleavage of CN triple bonds of organonitriles.
J Am Chem Soc
June 2004
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.
One Si-tethered diyne is coupled in one pot with three molecules of organonitriles promoted by a low-valent zirconocene species. Cleavage of one of the three CN triple bonds and cleavage of the two Si-C bonds take place to afford pyrrolo[3,2-c]pyridine derivatives after hydrolysis.
View Article and Find Full Text PDFOne-pot synthetic routes to multiply substituted indene derivatives by hydrolysis of zirconocene-mediated intermolecular coupling reactions of aromatic ketones and alkynes.
J Org Chem
February 2003
Peking University-Hokkaido University Joint Lab, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People's Republic of China.
Two one-pot multicomponent synthetic methods for highly substituted indenes are described. The intermolecular coupling of aromatic ketones with alkynes on low-valent zirconocene species generates oxazirconacyclopentenes, which upon hydrolysis with 20% HCl for 3 h afforded indene derivatives in good to excellent yields. Similarly, the pair-selective coupling of two identical or different alkynes bearing at least one aromatic substituent formed zirconacyclopentadienes.
View Article and Find Full Text PDFWant 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!