CC(CCCCCOC(C1C(C(OCCCCCC(C)C)=O)=CC=CC=1)=O)C.[CH2:29]=[CH:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.C(#N)C.[CH:40]#[N:41].CC#N>CCCCCCC.CCOCC.[Zn]>[C:31]1([CH:30]([CH3:29])[C:40]#[N:41])[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1A mixture of 1.5 g (+) Diop (2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, Aldrich Chemical Co.), 300 mg NiI2, 300 mg zinc dust, 2 ml commercial stabilized styrene, and 2 ml acetonitrile was stirred at 80° for 5 hr. then 250 μl HCN/CH3CN (11N) was added overnight by syringe pump. After addition of 2 ml styrene, 1 ml CH3CN and ca. 100 mg zinc dust another 400 μl HCN/CH3CN was added during eight hours. After addition of 4 ml styrene and 100 mg zinc addition of HCN/CH3CN at 50 μl/hr was continued overnight. The mixture was then diluted with 50 ml heptane and 25 ml ether. The mixture was filtered and the filtrate was concentrated to an oil which was diluted with an equal volume of toluene. The VPC analysis indicated that the two isomeric products PhCH(CN)CH3 and PhCH2CH2CN had been formed in approximately equal amounts. The PhCH(CN)CH3 was isolated by preparative VPC as described above to give 120 mg [α]D25 +1.1° C5.5% in CD3CN. An e.e. of about 10% is estimated based on the reported [α]D25 value of 10° for the pure isomer. The 1H nmr spectrum was as expected for PhCH(CN)CH3. The major product was apparently styrene polymer which hampered the isolation of the nitrile products.
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