费里尔重排反应
外观
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](http://upload.wikimedia.org/wikipedia/commons/thumb/7/7a/Ferrier_rearrangement.svg/800px-Ferrier_rearrangement.svg.png)
反应机理
[编辑]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
[编辑]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
[编辑]生成C-糖苷
[编辑]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](http://upload.wikimedia.org/wikipedia/commons/thumb/3/3c/Ferrier_rearrangement_C-glycoside.svg/400px-Ferrier_rearrangement_C-glycoside.svg.png)
含氮底物
[编辑]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](http://upload.wikimedia.org/wikipedia/commons/thumb/d/de/N-Ferrier_rearrangement.svg/403px-N-Ferrier_rearrangement.svg.png)
参见
[编辑]参考资料
[编辑]- ^ 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.
- ^ 2.0 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).
- ^ 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)
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ Kelly, David R. Catalytic tin radical mediated tricyclisations. Part 2. Journal of the Chemical Society Perkin Transactions 1. 2000: 1571. doi:10.1039/b000662i.
- ^ Donohoe, Timothy J. Synthesis of amino-sugars using the directed dihydroxylation reaction. Chemical Communications. 1999: 1733. doi:10.1039/a904991f.
- ^ 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.