title: Transition metal-mediated intramolecular [2+2+2] cycloisomerizations of cyclic triynes and enediynes.
abstract: [reaction: see text] Nitrogen-containing 15-membered triacetylenic macrocycles known as 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triynes (1) and enediynic macrocycles called 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3-ene-8,13-diynes (4 and 5) were satisfactorily prepared. [2+2+2] cycloisomerization processes catalyzed by transition metals were tested in the above-mentioned macrocycles. Readily available and familiar cyclotrimerization precatalysts were examined for efficiency. Among them, the RhCl(CO)(PPh(3))(2) complex was found to catalyze the cycloisomerization reaction giving the desired cycloadducts in high yields.
authors.affiliation: Department of Chemistry, Universitat de Girona, Campus de Montilivi, s/n. E-17071-Girona, Spain. anna.roglans@udg.es
authors.forename: Anna
authors.initials: A
authors.lastname: Torrent
authors.forename: Iván
authors.initials: I
authors.lastname: González
authors.forename: Anna
authors.initials: A
authors.lastname: Pla-Quintana
authors.forename: Anna
authors.initials: A
authors.lastname: Roglans
authors.forename: Marcial
authors.initials: M
authors.lastname: Moreno-Mañas
authors.forename: Teodor
authors.initials: T
authors.lastname: Parella
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D047028:Macrocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D019216:Metals, Heavy / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000480:Alkynes; D047028:Macrocyclic Compounds; D019216:Metals, Heavy; D009942:Organometallic Compounds; D010984:Platinum; D012238:Rhodium