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
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- 作者：Jianming Bao ; William D. Wulff ; Michael J. Fumo ; Eugene B. Grant ; Douglas P. Heller ; Mark C. Whitcomb ; and Siu-Man Yeung
- 刊名：Journal of the American Chemical Society
- 出版年：1996
- 出版时间：March 6, 1996
- 年：1996
- 卷：118
- 期：9
- 页码：2166 - 2181
- 全文大小：752K
- 年卷期：v.118,no.9(March 6, 1996)
- ISSN：1520-5126
文摘
The first examples of the reactions of Fischer carbene complexeswith 1,3-butadiynes are reported. Thesereactions are of interest since they provide new methods for thesynthesis of acetylenic substituted arenes and alsofor the synthesis of biaryls. The reactions of the complexes(CO)5Cr=C(OR1)R2[R1 = Me, n-Bu; R2 =phenyl,1-naphthyl, 1-cyclohexenyl] were investigated with the conjugateddiynes R3C
C-CCR3 [R3 =t-Bu, i-Pr, Ph].All of the carbene complexes will react with 1 equiv of the diyneto give good yields of acetylenic arenes 5, 19,and23, each with high selectivity for the regioisomer in whichthe substituent R3 on the diyne is incorporatedadjacentto the phenol function. The reactions of the alkynylarenes5, 19, and 23 with a second equivalentof carbene complexes,4, 16, and 22, respectively, generatethe bis-phenols 26, 31, and 33, withvarying amounts of five-membered-ringannulated compounds as side products. These side products are notseen with the cyclohexenyl complex 22 and canbe minimized to some extent for the phenyl complex 4a byproper control of the concentration and the temperature.Attempts to carry out benzannulations of both of the acetylenicfunctions in the 1,3-diyne concurrently by employing2 equiv of the carbene complex were not successful, and this issuspected to be due to the presence of a chromiumtricarbonyl group on the newly formed arene ring after the firstbenzannulation, such as in complex 34. Theconcurrentdouble benzannulation of a diyne can be achieved in an intramolecularfashion with the bis-carbene complex 39.The intramolecular process leads to a reversal in theregiochemistry of the second benzannulation producing theC2-symmetrical 2,2'-binaphthol 40from the reaction of complex 39 with the diyne 8along with the indenylnaphthalene41. The reaction of the optically pure bis-carbenecomplex 44 derived from(2R,3R)-butane-2,3-diol with diyne8gives a single diastereomer of the 2,2'-binaphthol 46.Chemical correlation with the known 2,2'-binaphthol 51revealsthat the biaryl axis in 46 has anS-configuration, which was predicted from an examination ofmodels.
C-CCR3 [R3 =t-Bu, i-Pr, Ph].All of the carbene complexes will react with 1 equiv of the diyneto give good yields of acetylenic arenes 5, 19,and23, each with high selectivity for the regioisomer in whichthe substituent R3 on the diyne is incorporatedadjacentto the phenol function. The reactions of the alkynylarenes5, 19, and 23 with a second equivalentof carbene complexes,4, 16, and 22, respectively, generatethe bis-phenols 26, 31, and 33, withvarying amounts of five-membered-ringannulated compounds as side products. These side products are notseen with the cyclohexenyl complex 22 and canbe minimized to some extent for the phenyl complex 4a byproper control of the concentration and the temperature.Attempts to carry out benzannulations of both of the acetylenicfunctions in the 1,3-diyne concurrently by employing2 equiv of the carbene complex were not successful, and this issuspected to be due to the presence of a chromiumtricarbonyl group on the newly formed arene ring after the firstbenzannulation, such as in complex 34. Theconcurrentdouble benzannulation of a diyne can be achieved in an intramolecularfashion with the bis-carbene complex 39.The intramolecular process leads to a reversal in theregiochemistry of the second benzannulation producing theC2-symmetrical 2,2'-binaphthol 40from the reaction of complex 39 with the diyne 8along with the indenylnaphthalene41. The reaction of the optically pure bis-carbenecomplex 44 derived from(2R,3R)-butane-2,3-diol with diyne8gives a single diastereomer of the 2,2'-binaphthol 46.Chemical correlation with the known 2,2'-binaphthol 51revealsthat the biaryl axis in 46 has anS-configuration, which was predicted from an examination ofmodels.