费里尔重排反应

提示：此条目的主题不是费里尔Ⅱ型重排反应。

费里尔重排反应（Ferrier rearrangement），由糖化学家罗伯特·费里尔（Robert J. Ferrier）首先报道。[1]

烯糖（2,3-不饱和糖苷）经亲核取代反应，生成烯丙基重排的产物。

典型的费里尔重排
典型的费里尔重排

反应机理

首先在路易斯酸（如氯化铟或三氟化硼）作用下，乙酸根离子离去，产生离域的氧杂烯丙基碳正离子(2)。接下来(2)原位与醇作用，生成2-糖苷的α-(3)和β-(4)异头物，同时双键迁移至3,4-位。[2]

例子

路易斯酸 醇 条件 结果
InCl3 甲醇 二氯甲烷溶剂 α:β = 7:1[3]
二噁烷 水 加热 75%产率[4]
SnCl4 甲醇 二氯甲烷溶剂，–78℃，10分钟 83%产率，α:β = 86:14[5]
BF3·O(C2H5)2 异丙醇 二氯甲烷溶剂，室温，24小时 95%产率[6][7]
ZnCl2 乙醇 甲苯溶剂，室温，30－60分钟 65–95%产率，α:β = 89:11[8][9]
BF3·O(C2H5)2 苄醇 二氯甲烷溶剂，–20℃至室温，1小时 98%产率[10]

改进法

生成C-糖苷

用硅烷替代醇，可得C-糖苷。如果硅烷为三乙基硅烷（R'=H），则反应后得到3,4-不饱和脱氧糖。[2]

利用费里尔重排生成C-糖苷
利用费里尔重排生成C-糖苷

含氮底物

1984年，Kozikowski 等报道了氮杂的费里尔重排，用于抗生素 streptazolin 的合成。[11]

氮杂费里尔重排
氮杂费里尔重排

参见

参考资料

  1. ^ Ferrier, Robert J. Unsaturated Carbohydrates. Part 21. A Carboxylic Ring Closure of a Hex-5-enopyranoside Derivative. J. Chem. Soc., Perkin Trans. 1. 1979: 1455–1458. doi:10.1039/P19790001455. 
  2. ^ 2.0 2.1 Konstantinović, Stanimir; et al. The Ferrier rearrangement as the key step in the synthesis of C7–C16-alkyl 2,3-dideoxy glucosides from glucose and C7–C16-alkanols (PDF). J.Serb.Chem.Soc. 2001, 66 (8): 499–505 [2009-10-09]. （原始内容存档 (PDF)于2011-10-08）. 
  3. ^ Boga, S. B.; Balasubramanian, K. K. Indium trichloride catalyzed Ferrier rearrangement – facile synthesis of 2,3-unsaturated glycosides. Arkivoc. 2004: 87–102 [2009-10-09]. （原始内容存档于2006-05-19）.  (open access publication)
  4. ^ Bert. Fraser- Reid; Bruno. Radatus. 4,6-Di-O-acetyl-aldehydo-2,3-dideoxy-D-erythro-trans-hex-2-enose. Probable reason for the 'al' in Emil Fischer's triacetyl glucal. J. Am. Chem. Soc. 1970, 92: 5288–5290. doi:10.1021/ja00720a087. 
  5. ^ Eleuterio Alvarez; Maria T. Diaz; Ricardo Perez; Jose L. Ravelo; Alicia Regueiro; Jose A. Vera; Dacil Zurita; Julio D. Martin. Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations. J. Org. Chem. 1994, 59: 2848. doi:10.1021/jo00089a034. 
  6. ^ Ferrier, R. J. Unsaturated carbohydrates. Part IX. Synthesis of 2,3-dideoxy-α-D-erythro-hex-2-enopyranosides from tri-O-acetyl-D-glucal. Journal of the Chemical Society C Organic. 1969: 570. doi:10.1039/J39690000570. 
  7. ^ Ferrier, R. J. Unsaturated carbohydrates. Part X. Epoxidations and hydroxylations of 2,3-dideoxy-α-D-hex-2-enopyranosides. The four methyl 4,6-di-O-acetyl-2,3-anhydro-α-D-hexopyranosides. Journal of the Chemical Society C Organic. 1969: 575. doi:10.1039/J39690000575. 
  8. ^ Kelly, David R. Catalytic tin radical mediated tricyclisations. Part 1. Monocyclisation studies. Journal of the Chemical Society Perkin Transactions 1. 2000: 1559. doi:10.1039/b000661k. 
  9. ^ Kelly, David R. Catalytic tin radical mediated tricyclisations. Part 2. Journal of the Chemical Society Perkin Transactions 1. 2000: 1571. doi:10.1039/b000662i. 
  10. ^ Donohoe, Timothy J. Synthesis of amino-sugars using the directed dihydroxylation reaction. Chemical Communications. 1999: 1733. doi:10.1039/a904991f. 
  11. ^ Kozikowski, AP, Pyeong-uk Park. Synthesis of 2-substituted δ3-piperidines: the nitrogen analog of the Ferrier rearrangement. An approach to streptazolin. J. Org. Chem. 1984, 49 (9): 1674–1676. doi:10.1021/jo00183a044.