Premium
Cyclotrimerization reactions of arynes and strained cycloalkynes
Author(s) -
Peña Diego,
Pérez Dolores,
Guitián Enrique
Publication year - 2007
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.20132
Subject(s) - aryne , palladium , catalysis , dimethyl acetylenedicarboxylate , cycloaddition , chemistry , metal , enantioselective synthesis , combinatorial chemistry , organic chemistry
The use of arynes and related species as substrates in metal‐catalyzed cycloaddition reactions leads to structurally interesting products. Palladium‐catalyzed cyclotrimerization of arynes provides a new method for the synthesis of polycyclic aromatic hydrocarbons. For instance, the chemoselective formal [2 + 2 + 2] cocycloaddition of 2,3‐triphenylynes with alkynes affords extended triphenylenes, which are good candidates to behave as liquid crystals. Cotrimerization of benzyne and electron‐deficient alkenes selectively affords dihydrophenanthrenes or ortho ‐olefinated biaryls depending on the catalytic system employed. The use of 2,2′‐bis(diphenylphosphino)‐1,1′‐binophythyl (BINAP)‐based palladium(0) catalysts in the cocyclotrimerization of 7‐methoxynaphthalyne and dimethyl acetylenedicarboxylate affords an enantiomerically enriched tetrasubstituted pentahelicene, the first example of a metal‐catalyzed enantioselective reaction involving arynes. Strained cyclic alkynes can also participate in the palladium‐catalyzed cyclotrimerization reactions, which again lead to structurally interesting products. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 326–333; 2007: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20132