有机化学 ›› 2000, Vol. 20 ›› Issue (5): 701-711. 上一篇    下一篇

研究论文

金属催化合成呋喃衍生物的最新进展

李林涛;麻生明   

  1. 中国科学院上海有机化学研究所.上海(200032);金属有机化学开放实验室
  • 发布日期:2000-10-25

Recent advances in metal-mediated synthesis of substituted furans

Li Lintao;Ma Shengming   

  1. Shanghai Inst Organ Chem., CAS.Shanghai(200032)
  • Published:2000-10-25

综述了近几年来利用金属催化合成多取代呋喃环的方法。分两大类介绍:一是通过对呋喃环进行结构改造,即呋喃金属试剂在过渡金属催化下与卤化物或酰氯发生偶联反应得到,或呋喃卤化物与金属试剂、烯烃、炔烃偶联得到;二是以非环状化合物为前体进行呋喃环的构筑,即在金属试剂催化下,1,2-联烯基酮、β-碘代-β-烯酮、叁键在α,β-、β,γ-、γ,δ-的炔酮、4-炔-2-烯醇可以关环得到多取代的呋喃产物。此外,在Ru~2(OAc)~4催化下,α-叠氮酮与炔烃反应得到金属卡宾中间体,然后关环也可得到取代呋喃产物。

关键词: 过渡金属化合物, 过渡金属络合物, 金属试剂, 金属催化剂, 呋喃P

The regiospecific synthesis of substituted furans by metal-catalyzed methodologies is reviewed. The whole review consists two parts. (1) Methodologies based on preformed furans. Furanyl metal reagents (M=Sn, B, Zn, Mn etc) undergo transition metal-catalyzed cross coupling reaction with organic halides or acyl chlorides to afford the substituted furans. On the another hand, furanyl halides can also undergo cross coupling reaction with orgnometallic reagents or termial alkynes to afford functionalized furans. Under the catalysis of Pd(0), furanyl halides can also react with alkenes to produce alkenyl substituted furans. The C-H activation reaction of furans with RuH~2(CO)PPh~3 directly produced furanyl ruthenium intermediates, which can further react with certain silylsubstituted 1-alkynes to afford 3-substituted furans. The C-H bond activation occurred regiospecifically the 3-positions. (2) Methodologies based on the cyclization reaction of acyclic compounds. The most efficient way to synthesize furans is the cyclization of the corresponding acyclic precursors, which provides the diversity, efficiency, and selectivity for the substituted furans synthesized. Under the catalysis of Ru(Ⅱ) or Ag(Ⅰ), 1,2-allenyl ketone can undergo cycloisomerization to afforded 3-unsubstituted furans. Recently Pd(0)-catalyzed coupling- cyclization reactions of organic halides and 1,2-allenyl ketones were also developed to afford polysubstituted furans. The diversity of furan thus synthesized depends on the type of organic halides as well as the substitution patterns of 1,2-allenyl ketones. Under the catalysis of Pd complexes, β-iodo-β-enone can undergo oxidative addition-cyclization or dimerization reaction to produce furans. Under the catalysis of Pd, another type of acyclic starting material suitable for the synthesis of furan is alkynones, the carbon-carbon triple bond can be located at α, β-, β, γ-, and γ,δ-positions. Both cycloisomerization and two-component coupling-cyclization have be金属催化合成? $609$ADD

Key words: TRANSITION METAL COMPOUND, TRANSITION METAL COMPLEX, METAL CATALYST, FURAN P

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