REACTIONS OF DIMETHYLTITANOCENE WITH ALKYNES AND NITRILES

被引:64
作者
PETASIS, NA
FU, DK
机构
关键词
D O I
10.1021/om00033a059
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Thermolysis of dimethyltitanocene in the presence of internal alkynes formed the corresponding titanacyclobutenes cleanly and efficiently. This reaction was shown to be first order in dimethyltitanocene with a primary kinetic isotope effect. When diphenylacetylene was reacted with dimethyltitanocene at lower temperatures, a competitive migratory insertion process took place, forming a vinyl-substituted titanocene species. An analogous reaction with 2 equiv of nitriles formed the known 1,3-diaza-2-titana-1,4-cyclohexadiene derivatives.
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页码:3776 / 3780
页数:5
相关论文
共 59 条
  • [51] SPIRO-FUSED 2,5-CYCLOHEXADIENONES FROM THERMAL 1,3-SHIFTS IN QUINOL VINYL ETHERS - REACTIONS IN NONBENZENOID SYSTEMS AND LIMITATIONS OF THE CHEMISTRY
    SWENTON, JS
    BRADIN, D
    GATES, BD
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (21) : 6156 - 6163
  • [52] TITANIUM-CATALYZED OLEFIN METATHESIS
    TEBBE, FN
    PARSHALL, GW
    OVENALL, DW
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (17) : 5074 - 5075
  • [53] OLEFIN HOMOLOGATION WITH TITANIUM METHYLENE-COMPOUNDS
    TEBBE, FN
    PARSHALL, GW
    REDDY, GS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (11) : 3611 - 3613
  • [54] TITANACYCLOBUTENES
    TEBBE, FN
    HARLOW, RL
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (19) : 6149 - 6151
  • [55] PHOTOCHEMISTRY OF TITANACYCLOBUTANES - EVIDENCE FOR A METAL-CENTERED 1,4-BIRADICAL INTERMEDIATE
    TUMAS, W
    WHEELER, DR
    GRUBBS, RH
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (20) : 6182 - 6184
  • [56] TUMAS W, 1990, ANGEW CHEM, V102, P89
  • [57] THE FORMATION OF TITANOCENE-METHYLENE COMPLEXES IN 1,3-DITITANACYCLOBUTANES
    VANDEHEISTEEG, BJJ
    SCHAT, G
    AKKERMAN, OS
    BICKELHAUPT, F
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1986, 310 (02) : C25 - C28
  • [58] VONCLAUSS K, 1962, LIEBIGS ANN CHEM, P8
  • [59] 1992, 204TH NAT M AM CHEM