Dealkylation of Ethers. A Review.

[Rhodium]

Dealkylation of Ethers. A Review.
B.C. Ranu & S. Bhar

Org. Prep. Proced. Int. 28(4), 371-409 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/ether.dealkylation.review.pdf)
(Scanned by FreakyDMT)

Introduction

I) Dealkylation of Alkyl and Aryl Ethers

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">1) Acidic Reagents
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Hydrobromic Acid in Presence of Phase Transfer Catalyst
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Boron Tribromide
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Boron Trihalide - Methyl Sulfide Complex
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">d) Boron Tribromide - Sodium Iodide - 15-crown-5
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">e) Dimethylboron Bromide
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">f) Boron Triiodide-N.N-Diethylaniline Complex
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">2) Basic Reagents
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Sodium Salt of N-Methylaniline
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Sodium Ethanethiolate
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Sodium Benzylselenoate
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">3) Miscellaneous Reagents
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Trimethylsilyl Iodide
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Chlorotrimethylsilane und Acetic Anhydride
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Zinc and Acyl Chloride
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">d) Lithium Chloride in DMF
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">e) Potassium in THF - A Reductive Cleavage Agent
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">f) Low Valent Titanium in THF - A Reductive Dealkoxylation
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">g) Metallic Nitrate Supported on Silica Gel - An Oxidative Cleavage Reaction
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">h) Nitrogen Dioxide - An Oxidative Cleavage Reagent

II) Dealkylation Of Allyl And Benzyl Ethers

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Aluminium Chloride - N,N-Dimethylaniline
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Cationic Iridium Complex
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Samarium(III)Chloride-Catalyzed Electrolysis
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">d) Low Valent Titanium
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">e) Zirconocene Dichloride - n-BuLi
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">f) PdCl₂ - CuCl - DMF - H₂O - O₂
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">g) Pd(Ph₃)₄ - NaBH₄
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">h) N-Bromosuccinimide
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">i) Boron Trichloride - Methyl Sulfide Complex

III) Cleavage Of Cyclic Ethers

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Palladium(II)Complexes in Presence of Organotin Halides
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Sodium Iodide - Acyl Chloride   
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Platinum Complexes
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">d) Aluminum Chloride - Sodium Iodide - Acetonitrile
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">e) Zinc - Acyl Chloride
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">f) Trimethylsilyl Iodide    

IV) Selectivity in Dealkylation Of Ethers

https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Selective Dealkylation of Alkyl Ether   
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">b) Selective Dealkylation of Aryl Ether   
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">c) Selective Dealkylation of Allyl Ether   
https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif" title="View this image">a) Selective Dealkylation of Benzyl Ether   

V) Conclusion

VI) References