费里尔重排反应

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]

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]

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]

参见

化学反应列表

参考资料

^ 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.

[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.

[Konstantinović-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.

[Kozikowski1984-11] 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.

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