REACTION OF FISCHER CARBENE COMPLEXES WITH 1,3-BUTADIYNES - A NEW STRATEGEM FOR BIARYL SYNTHESIS WITH CONSTRUCTION OF THE BIARYL BOND PRECEDING SYNTHESIS OF THE ARENES

Citation
Jm. Bao et al., REACTION OF FISCHER CARBENE COMPLEXES WITH 1,3-BUTADIYNES - A NEW STRATEGEM FOR BIARYL SYNTHESIS WITH CONSTRUCTION OF THE BIARYL BOND PRECEDING SYNTHESIS OF THE ARENES, Journal of the American Chemical Society, 118(9), 1996, pp. 2166-2181
Citations number
39
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
ISSN journal
0002-7863
Volume
118
Issue
9
Year of publication
1996
Pages
2166 - 2181
Database
ISI
SICI code
0002-7863(1996)118:9<2166:ROFCCW>2.0.ZU;2-D
Abstract
The first examples of the reactions of Fischer carbene complexes with 1,3-butadiynes are reported. These reactions are of interest since the y provide new methods for the synthesis of acetylenic substituted aren es and also for the synthesis of biaryls. The reactions of the complex es (CO)(5)Cr=C(OR(1))R(2)[R(1) = Me, n-Bu; R(2) = phenyl, 1-naphthyl, 1-cyclohexenyl] were investigated with the conjugated diynes R(3)C=C-C =CR(3)[R(3) = t-Bu, i-Pr, Ph]. All of the carbene complexes will react with 1 equiv of the diyne to give good yields of acetylenic arenes 5, 19, and 23, each with high selectivity for the regioisomer in which t he substituent R(3) on the diyne is incorporated adjacent to the pheno l function. The reactions of the alkynylarenes 5, 19, and 23 with a se cond equivalent of carbene complexes, 4, 16, and 22, respectively, gen erate the bis-phenols 26, 31, and 33, with varying amounts of five-mem bered-ring annulated compounds as side products. These side products a re not seen with the cyclohexenyl complex 22 and can be minimized to s ome extent for the phenyl complex 4a by proper control of the concentr ation and the temperature. Attempts to carry out benzannulations of bo th of the acetylenic functions in the 1,3-diyne concurrently by employ ing 2 equiv of the carbene complex were not successful, and this is su spected to be due to the presence of a chromium tricarbonyl group on t he newly formed arene ring after the first benzannulation, such as in complex 34. The concurrent double benzannulation of a diyne can be ach ieved in an intramolecular fashion with the bis-carbene complex 39. Th e intramolecular process leads to a reversal in the regiochemistry of the second benzannulation producing the C-2-symmetrical 2,2'-binaphtho l 40 from the reaction of complex 39 with the diyne 8 along with the i ndenylnaphthalene 41. The reaction of the optically pure bis-carbene c omplex 44 derived from (2R,3R)-butane-2,3-diol with diyne 8 gives a si ngle diastereomer of the 2,2'-binaphthol 46. Chemical correlation with the known 2,2'-binaphthol 51 reveals that the biaryl axis in 46 has a n S-configuration, which was predicted from an examination of models.