Premium
Zirconocene‐Mediated, High‐Yielding Macrocyclizations of Silyl‐Terminated Diynes
Author(s) -
Schafer Laurel L.,
Nitschke Jonathan R.,
Mao Shane S. H.,
Liu FengQ.,
Harder Gabriele,
Haufe Markus,
Tilley T. Don
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020104)8:1<74::aid-chem74>3.0.co;2-p
Subject(s) - silylation , zirconium , yield (engineering) , chemistry , dilution , metal , polymer chemistry , materials science , organic chemistry , catalysis , metallurgy , physics , thermodynamics
A series of silyl‐terminated diynes of varying lengths and substitution patterns have been prepared. These diynes undergo zirconocene coupling with selective formation of trimeric macrocycles from linear alkynes, while nonlinear diynes give cyclodimeric products. The length of the linear diynes can be increased for the preparation of macrocycles with large nanoscale cavities. Reaction of the zirconium‐containing macrocycles with acid results in the synthesis of metal‐free cyclophanes. All of these macrocycles were prepared in multigram quantities, in the absence of high‐dilution conditions, to give products in >75 % yield that are easily purified as crystalline solids.