请输入您要查询的百科知识：

　

词条 Ferrier rearrangement
释义

  1. Mechanism

  2. Examples

  3. Modifications

      Forming of C-glycosides    Nitrogen analogue  

  4. References

{{distinguish|text=the Ferrier carbocyclization or Ferrier II reaction, a reaction discovered by the same chemist}}

The Ferrier rearrangement is an organic reaction that involves a nucleophilic substitution reaction combined with an allylic shift in a glycal (a 2,3-unsaturated glycoside). It was discovered by the carbohydrate chemist Robert J. Ferrier.[1][2]

Mechanism

In the first step, a delocalized allyloxocarbenium ion (2) is formed, typically with the aid of a Lewis acid like indium(III) chloride or boron trifluoride. This ion reacts in situ with an alcohol, yielding a mixture of the α (3) and β (4) anomers of the 2-glycoside, with the double bond shifted to position 3,4.[3]

Examples

Lewis acid Alcohol Conditions Results
InCl3 methanol in dichloromethane α:β = 7:1[4]
dioxane water heating 75% yield[5]
SnCl4 methanol in dichloromethane, –78 °C, 10 min 83% yield, α:β = 86:14[6]
BF3·O(C2H5)2 isopropanol in dichloromethane, RT, 24 hr 95% yield[7][8]
ZnCl2 ethanol in toluene, RT, 30–60 min 65–95% yield, α:β = 89:11[9][10]
BF3·O(C2H5)2 benzyl alcohol in dichloromethane, –20 °C to RT, 1 hr 98% yield[11]

Modifications

Forming of C-glycosides

By replacing the alcohol with a silane, C-glycosides can be formed. With triethylsilane (R'=H), the reaction yields a 2,3-unsaturated deoxy sugar.[3]

Nitrogen analogue

An analogous reaction with nitrogen as the heteroatom was described in 1984 for the synthesis of the antibiotic substance streptazolin.[12]

References

1. ^{{cite journal|last=Ferrier|first=Robert J.|year=1979|title=Unsaturated Carbohydrates. Part 21. A Carboxylic Ring Closure of a Hex-5-enopyranoside Derivative|journal=J. Chem. Soc. Perkin Trans. 1|pages=1455–1458|doi=10.1039/P19790001455}}
2. ^{{cite journal|last1=Ferrier|first1=Robert J.|last2=Zubkov|first2=O. A.|journal=Org. React.|year=2003|volume=62|doi=10.1002/0471264180.or062.04|title=Transformation of Glycals into 2,3-Unsaturated Glycosyl Derivatives|isbn=0-471-26418-0}}
3. ^1 {{cite journal|last=Konstantinović|first=Stanimir|year=2001|title=The Ferrier rearrangement as the key step in the synthesis of C7–C16-alkyl 2,3-dideoxy glucosides from glucose and C7–C16-alkanols|journal=J.Serb.Chem.Soc.|volume=66|issue=8|pages=499–505|url=http://www.shd.org.rs/JSCS/Vol66/No8/V66-No8-01.pdf|display-authors=etal}}
4. ^{{cite journal|last=Boga|first=S. B.|author2=Balasubramanian, K. K.|year=2004|title=Indium trichloride catalyzed Ferrier rearrangement – facile synthesis of 2,3-unsaturated glycosides|journal=Arkivoc|pages=87–102|url=http://www.arkat-usa.org/ark/journal/2004/I08_Narasimhan/1099/1099.asp}} (open access publication)
5. ^{{cite journal|journal=J. Am. Chem. Soc.|year=1970|volume=92|pages=5288–5290|doi=10.1021/ja00720a087|title=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|author1=Bert. Fraser- Reid |author2=Bruno. Radatus |issue=17}}
6. ^{{cite journal|journal=J. Org. Chem.|year=1994|volume=59|pages=2848|doi=10.1021/jo00089a034|title=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|author1=Eleuterio Alvarez |author2=Maria T. Diaz |author3=Ricardo Perez |author4=Jose L. Ravelo |author5=Alicia Regueiro |author6=Jose A. Vera |author7=Dacil Zurita |author8=Julio D. Martin |issue=10}}
7. ^{{cite journal|journal=Journal of the Chemical Society C: Organic|year=1969|pages=570|doi=10.1039/J39690000570|title=Unsaturated carbohydrates. Part IX. Synthesis of 2,3-dideoxy-α-D-erythro-hex-2-enopyranosides from tri-O-acetyl-D-glucal|author=Ferrier, R. J.|last2=Prasad|first2=N.|issue=4}}
8. ^{{cite journal|date=|journal=Journal of the Chemical Society C: Organic|year=1969|pages=575|doi=10.1039/J39690000575|title=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|author=Ferrier, R. J.|last2=Prasad|first2=N.|issue=4}}
9. ^{{cite journal|last2=Picton|first2=Mark R.|year=2000|title=Catalytic tin radical mediated tricyclisations. Part 1. Monocyclisation studies|journal=Journal of the Chemical Society, Perkin Transactions 1|volume=|issue=10|pages=1559|doi=10.1039/b000661k|author=Kelly, David R.}}
10. ^{{cite journal|last2=Picton|first2=Mark R.|year=2000|title=Catalytic tin radical mediated tricyclisations. Part 2.|journal=Journal of the Chemical Society, Perkin Transactions 1|volume=|issue=10|pages=1571|doi=10.1039/b000662i|author=Kelly, David R.}}
11. ^{{cite journal|year=1999|journal=Chemical Communications|volume=|pages=1733|doi=10.1039/a904991f|title=Synthesis of amino-sugars using the directed dihydroxylation reaction|author=Donohoe, Timothy J.|last2=Blades|first2=Kevin|last3=Helliwell|first3=Madeleine|issue=17}}
12. ^{{cite journal| author = Kozikowski, AP, Pyeong-uk Park| title = Synthesis of 2-substituted .DELTA.3-piperidines: the nitrogen analog of the Ferrier rearrangement. An approach to streptazolin| journal = J. Org. Chem.| year = 1984| volume = 49| issue = 9| pages = 1674–1676| doi =10.1021/jo00183a044}}

3 : Carbohydrate chemistry|Rearrangement reactions|Name reactions
随便看

　

开放百科全书收录14589846条英语、德语、日语等多语种百科知识，基本涵盖了大多数领域的百科知识，是一部内容自由、开放的电子版国际百科全书。

　

Copyright © 2023 OENC.NET All Rights Reserved
京ICP备2021023879号 更新时间：2024/11/10 22:11:59