Stereodefined Synthesis of a New Type of 1,3-Dienes by Ligand-Controlled Carbon−Carbon and Carbon−Heteroatom Bond Formation in Nickel-Catalyzed Reaction of Diaryldichalcogenides with Alkyn
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- 作者：Valentine P. Ananikov ; Nikolay V. Orlov ; Mikhail A. Kabeshov ; Irina P. Beletskaya ; Zoya A. Starikova
- 刊名：Organometallics
- 出版年：2008
- 出版时间：August 25, 2008
- 年：2008
- 卷：27
- 期：16
- 页码：4056-4061
- 全文大小：244K
- 年卷期：v.27,no.16(August 25, 2008)
- ISSN：1520-6041
文摘
We have found that ligand control over the carbon−carbon and carbon−heteroatom bond formation on the nickel center provides an easy and convenient route to symmetrical (minor) and unsymmetrical (major) isomers of sulfur- and selenium-substituted 1,3-dienes. The unsymmetrical product is a new type of 1,4-substituted conjugated diene, which was readily synthesized from alkynes and diaryldichalcogenides. The unique feature of this developed one-pot transformation is total stereodefined synthesis of the diene skeleton, controlling not only the configuration of the double bond but also the s-gauche conformation of the central C−C bond. The mechanistic study revealed the key feature of alkyne insertion into the Ni−E and Ni−C bonds (E = S, Se), which governs the direction of the chemical transformation.