138205-99-9Relevant academic research and scientific papers
Metallometallation of allenes: an exploratory study
Singh, Shankar,Oehlshlager, Allan C.
, p. 1872 - 1880 (2007/10/02)
Reaction of either n-Bu3SnCu(CN)Li (8) or (n-Bu3Sn)2Cu(CN)Li2 (9) with 1,2-undecadiene gave 71-92percent of a (Z/E) mixture of 1-tri-n-butylstannyl-2-undecene (27) accompanied by 8-32percent of a mixture of (E)-2-tri-n-butylstannyl-2-undecene (28) and 2-tri-n-butylstannyl-1-undecene (29).When the above reactions were warmed to 0 deg C, 28 and 29 were the major products.The mixed cuprates, 10-14, gave the mixtures rich in vinylstannanes, 28 and 29, along with 27.Addition of Sn-Al reagents, 15 and 16, or Sn-B reagents, 18 and 19, to 1,2-undecadiene in the presence of 5 molpercent of CuCN or CoCl2*(PPh3)2 provided mixtures rich in vinylstannanes, 28 and 29.However, with 1 equiv. of CuCN, mixtures rich in allylstannanes 27 were obtained.Reaction of 5-hydroxy-1,2-pentadiene with Sn-Al reagents, 15 and 16, gave 53-61percent of a single 5-hydroxy-2-tri-n-butylstannyl-1-pentene (32) in the presence of 5 molpercent of CoCl2*(PPh3)2.The stannylcopper adducts generated in the reaction of 1,2-undecadiene and 8 or 9 were treated with iodomethane to give 55-78percent of a (Z/E: 67/33) mixture of 1-tri-n-butylstannyl-2-methyl-2-undecene (33).Addition of mixed silylcuprates, 21, 22, and 23, to 1,2-undecadiene gave mixtures rich in (E)-2-dimethylphenylsilyl-2-undecene (35) and 2-dimethylphenylsilyl-1-undecne (36).A rationale for the 'putative adducts' formation is also presented. Key words: Sn-Cu, Sn-Al, Sn-B reagents; putative adducts.
