Tris acetylacetonato cobalt-Diethylaluminum Chloride-NORPHOS

2- diols is available from methyl mandelate by addition of the corresponding substituted arylmagnesium bromides or aryllithium reagents.  

Related Reagents. 10,2-Camphorsultam (/ )-2-t-Butyl-6-methyl-4//-l,3-dioxin-4-one (/ )-(+)-(t)-Butyl 2-(/ -Tolysulfin-yl)propionate Chloro(cyclopentadienyl)bis[3-0-( 1,2 5,6-do-0-isopropylidene-a-D-glucofuranosyl)]titanium lO-Dicyclohexyl-sulfonamidoisobomeol Diisopinocampheylboron Trifluoro-methanesulfonate (R,/ )-2,5-Dimethylborolane 2-Hydroxy- 

4-Benzyl-2-oxazolidinone 3-Propionylthiazolidine-2-thione (R,R)-1,2-Diphenyl-1,2-diaminoethane AA/ -Bis[3,5-bis- 

Physical Data see Diethylaluminum Chloride and (+)-trans-(2S,3S)-Bis(diphenylphosphino)bicyclo[2.2.1 ]hept-5-ene (NORPHOS). 

Preparative Methods synthesized in situ from the three components, using a 1.5 excess of the chelate phosphine the components are commercially available or can be easily prepared. 

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TRIS(ACETYLACETONATO)COBALT-DIETHYLALUMINUM CHLORIDE-NORPHOS... 

Tris(acetylacetonato)cobalt-Diethylaluminum Chloride-NORPHOS... 

Preparation of the in situ Catalyst and Catalytic Reaction. (This is a typical procedure for norbomadiene and phenylacetylene or 1-hexyne). Tris(acetylacetonato)cobalt (7.1 mg, 2.0x10 mmol) and (+)-NORPHOS (13.8 mg, 3.0 x 10 mmol) are dissolved in 1 ml of THF under dry nitrogen, using standard Schlenk techniques. Norbomadiene (1.0 mL, 10.0 mmol) and 10 mmol of phenylacetylene or 1-hexyne are added. The reaction is started by addition of 5 mL of a IM solution of diethylaluminum chloride in hexane. The reaction mixture is kept at 35 °C for 4 h. Then 5 mL of isopropanol are added and the volatile components are removed in vacuum. The oily residue is distilled at 80 °C in high vacuum in a Kugelrohr apparatus. Chemical yield >99% enantiomeric excess 98.4-99.6% for (+)-4-phenyldeltacyclene and 97.6-98.0% for (+)-4-n-butyldeltacyclene. 

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