Transition metal-mediated intramolecular [2+2+2] cycloisomerizations of cyclic triynes and enediynes.
[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.
Torrent
Anna
A
Department of Chemistry, Universitat de Girona, Campus de Montilivi, s/n. E-17071-Girona, Spain. anna.roglans@udg.es
González
Iván
I
Pla-Quintana
Anna
A
Roglans
Anna
A
Moreno-Mañas
Marcial
M
Parella
Teodor
T
Benet-Buchholz
Jordi
J
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
D000480:Alkynes; D047028:Macrocyclic Compounds; D019216:Metals, Heavy; D009942:Organometallic Compounds; D010984:Platinum; D012238:Rhodium