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Molybdenum chloride catalysts for Z-selective olefin metathesis reactions.
Koh, Ming Joo; Nguyen, Thach T; Lam, Jonathan K; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R; Hoveyda, Amir H.
Afiliação
  • Koh MJ; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
  • Nguyen TT; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
  • Lam JK; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
  • Torker S; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
  • Hyvl J; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
  • Schrock RR; Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
  • Hoveyda AH; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Nature ; 542(7639): 80-85, 2017 02 02.
Article em En | MEDLINE | ID: mdl-28114300
The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.
Assuntos

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Cloretos / Alcenos / Molibdênio Idioma: En Ano de publicação: 2017 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Cloretos / Alcenos / Molibdênio Idioma: En Ano de publicação: 2017 Tipo de documento: Article