The Vespiary

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)

(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)1) Acidic Reagents
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)a) Hydrobromic Acid in Presence of Phase Transfer Catalyst
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Boron Tribromide
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Boron Trihalide - Methyl Sulfide Complex
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)d) Boron Tribromide - Sodium Iodide - 15-crown-5
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)e) Dimethylboron Bromide
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)f) Boron Triiodide-N.N-Diethylaniline Complex
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)2) Basic Reagents
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)a) Sodium Salt of N-Methylaniline
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Sodium Ethanethiolate
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Sodium Benzylselenoate
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)3) Miscellaneous Reagents
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)a) Trimethylsilyl Iodide
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Chlorotrimethylsilane und Acetic Anhydride
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Zinc and Acyl Chloride
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)d) Lithium Chloride in DMF
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)e) Potassium in THF - A Reductive Cleavage Agent
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)f) Low Valent Titanium in THF - A Reductive Dealkoxylation
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)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)(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)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)a) Aluminium Chloride - N,N-Dimethylaniline
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Cationic Iridium Complex
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Samarium(III)Chloride-Catalyzed Electrolysis
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)d) Low Valent Titanium
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)e) Zirconocene Dichloride - n-BuLi
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)f) PdCl₂ - CuCl - DMF - H₂O - O₂
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)g) Pd(Ph₃)₄ - NaBH₄
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)h) N-Bromosuccinimide
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)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)a) Palladium(II)Complexes in Presence of Organotin Halides
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Sodium Iodide - Acyl Chloride   
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Platinum Complexes
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)d) Aluminum Chloride - Sodium Iodide - Acetonitrile
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)e) Zinc - Acyl Chloride
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)f) Trimethylsilyl Iodide    

IV) Selectivity in Dealkylation Of Ethers

(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)a) Selective Dealkylation of Alkyl Ether   
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)b) Selective Dealkylation of Aryl Ether   
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)c) Selective Dealkylation of Allyl Ether   
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000453324-file_oxgw.gif)a) Selective Dealkylation of Benzyl Ether   

V) Conclusion

VI) References