Theoretical Studies on Ru-Catalyzed Pauson-Khand-Type [2+2+1] and   Related [2+2+1+1] Cycloadditions

doi:10.1021/om8004178

CORC > 北京大学 > 化学与分子工程学院

	Theoretical Studies on Ru-Catalyzed Pauson-Khand-Type [2+2+1] and Related [2+2+1+1] Cycloadditions
	Wang, Can ; Wu, Yun-Dong
刊名	organometallics
	2008
关键词	TRANSITION-METAL CARBONYLS TRANSIENT INFRARED-SPECTROSCOPY AB-INITIO PSEUDOPOTENTIALS FORMAL TOTAL-SYNTHESIS ORGANIC-SYNTHESIS ALKYNE COMPLEXES ATOM ECONOMY VIBRATIONAL-SPECTRA MOLECULAR-STRUCTURE BOND-CLEAVAGE
DOI	10.1021/om8004178
英文摘要	Density functional theory (DFT) calculations have been carried out to understand the mechanism of the Ru(3)(CO)(12)-catalyzed Pauson-Khand-type [2+2+ 1] reaction and related [2+2+1+1] cycloadditions. The geometries were optimized using the BP86/6-31G(SDD for Ru) method, and the energies were evaluated with the 6-311+G(SDD) basis set. We found that these reactions are initiated by a CO-alkyne coupling, forming a ruthenacyclobutenone intermediate, and the widely accepted alkene-alkyne coupling pathway has a much higher activation energy. In the intermolecular reaction between alkene and alkyne, the formation of quinones and hydroquinones through [2+2+1+1] cycloadditions is more favorable than the Pauson-Khand-type reaction, while the intramolecular reaction with 1,6-enyne leads to a favorable Pauson-Khand-type reaction. These results are in agreement with experimental observations. For the [2+2+1+1] cycloadditions we found that the formation of quinones is favored over the formation of hydroquinones due to the preferred insertion of alkynes, which can be attributed to the preferred orbital interaction between the pi orbital of the alkyne moiety and the d orbital of the metal center.; Chemistry, Inorganic & Nuclear; Chemistry, Organic; SCI(E); EI; 4; ARTICLE; 23; 6152-6162; 27
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/247701]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Can,Wu, Yun-Dong. Theoretical Studies on Ru-Catalyzed Pauson-Khand-Type [2+2+1] and Related [2+2+1+1] Cycloadditions[J]. organometallics,2008.
APA	Wang, Can,&Wu, Yun-Dong.(2008).Theoretical Studies on Ru-Catalyzed Pauson-Khand-Type [2+2+1] and Related [2+2+1+1] Cycloadditions.organometallics.
MLA	Wang, Can,et al."Theoretical Studies on Ru-Catalyzed Pauson-Khand-Type [2+2+1] and Related [2+2+1+1] Cycloadditions".organometallics (2008).