Nucleophilic acyl substitutions of esters with protic nucleophiles mediated by amphoteric, oxotitanium, and vanadyl species

被引:45
作者
Chen, CT [1 ]
Kuo, JH [1 ]
Ku, CH [1 ]
Weng, SS [1 ]
Liu, CY [1 ]
机构
[1] Natl Taiwan Normal Univ, Dept Chem, Taipei 11650, Taiwan
关键词
D O I
10.1021/jo0484878
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
[GRAPHICS] A diverse array of oxometallic species were examined as catalysts in nucleophilic acyl substitution (NAS) reactions of methyl (or ethyl) esters with protic nucleophiles. Among them, oxotitanium acetylacetonate (TiO(acac)(2)) and vanadyl chloride (VOCl2-(THF)(x)) served as the most efficient and water-tolerant catalysts. Transesterifications of methyl and/or ethyl esters with functionalized (including acid- or base-sensitive) 1degrees and 2degrees alcohols can be carried out chemoselectively in refluxed toluene or xylene in a 1:1 substrate stoichiometry using 1 mol % catalyst loading. The resultant products were furnished in 85-100% yields by simple aqueous workup to remove water-soluble catalysts. The new NAS protocol is also amenable to amines and thiols in 74-91% yields, albeit with higher loading (2.5 equiv) of protic nucleophiles. Representative examples of commercial interests such as Padimate 0 and antioxidant additives for plastics were also examined to demonstrate their practical applications. A 1:1 adduct between TiO(acac)2 and a given 1-octadecanol was identified as (C18H37O)(2)Ti(acac)(2) and was responsible for its subsequent NAS of methyl esters.
引用
收藏
页码:1328 / 1339
页数:12
相关论文
共 86 条
  • [21] DEWOLFE RH, 1974, SYNTHESIS-STUTTGART, P153
  • [22] Ester interchange by means of the grignard complex
    Frank, RL
    Davies, HR
    Drake, SS
    McPherson, JB
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1944, 66 : 1509 - 1510
  • [23] GODL S, 1984, MONATSH CHEM, V115, P1185
  • [24] Efficient transesterification/acylation reactions mediated by N-heterocyclic carbene catalysts
    Grasa, GA
    Güveli, T
    Singh, R
    Nolan, SP
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (07) : 2812 - 2819
  • [25] N-heterocyclic carbenes as versatile nucleophilic catalysts for transesterification/acylation reactions
    Grasa, GA
    Kissling, RM
    Nolan, SP
    [J]. ORGANIC LETTERS, 2002, 4 (21) : 3583 - 3586
  • [26] GROBE J, 1984, Z NATURFORSCH B, V39, P808
  • [27] REACTIONS OF ISOPROPENYL ACETATE
    HAGEMEYER, HJ
    HULL, DC
    [J]. INDUSTRIAL AND ENGINEERING CHEMISTRY, 1949, 41 (12): : 2920 - 2924
  • [28] Organorhenium oxides
    Herrmann, WA
    Kuhn, FE
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (04) : 169 - 180
  • [29] SYNTHESES AND STRUCTURES OF NEW 2,2'-BIPYRIDINE COMPLEXES OF NIOBIUM, MOLYBDENUM, TUNGSTEN, AND RHENIUM IN HIGH OXIDATION-STATES
    HERRMANN, WA
    THIEL, WR
    HERDTWECK, E
    [J]. CHEMISCHE BERICHTE-RECUEIL, 1990, 123 (02): : 271 - 276
  • [30] Catalytic asymmetric coupling of 2-naphthols by chiral tridentate oxovanadium(IV) complexes
    Hon, SW
    Li, CH
    Kuo, JH
    Barhate, NB
    Liu, YH
    Wang, Y
    Chen, CT
    [J]. ORGANIC LETTERS, 2001, 3 (06) : 869 - 872