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)
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Introduction

I) Dealkylation of Alkyl and Aryl Ethers

1) Acidic Reagents
a) Hydrobromic Acid in Presence of Phase Transfer Catalyst
b) Boron Tribromide
c) Boron Trihalide - Methyl Sulfide Complex
d) Boron Tribromide - Sodium Iodide - 15-crown-5
e) Dimethylboron Bromide
f) Boron Triiodide-N.N-Diethylaniline Complex
2) Basic Reagents
a) Sodium Salt of N-Methylaniline
b) Sodium Ethanethiolate
c) Sodium Benzylselenoate
3) Miscellaneous Reagents
a) Trimethylsilyl Iodide
b) Chlorotrimethylsilane und Acetic Anhydride
c) Zinc and Acyl Chloride
d) Lithium Chloride in DMF
e) Potassium in THF - A Reductive Cleavage Agent
f) Low Valent Titanium in THF - A Reductive Dealkoxylation
g) Metallic Nitrate Supported on Silica Gel - An Oxidative Cleavage Reaction
h) Nitrogen Dioxide - An Oxidative Cleavage Reagent

II) Dealkylation Of Allyl And Benzyl Ethers

a) Aluminium Chloride - N,N-Dimethylaniline
b) Cationic Iridium Complex
c) Samarium(III)Chloride-Catalyzed Electrolysis
d) Low Valent Titanium
e) Zirconocene Dichloride - n-BuLi
f) PdCl₂ - CuCl - DMF - H₂O - O₂
g) Pd(Ph₃)₄ - NaBH₄
h) N-Bromosuccinimide
i) Boron Trichloride - Methyl Sulfide Complex

III) Cleavage Of Cyclic Ethers

a) Palladium(II)Complexes in Presence of Organotin Halides
b) Sodium Iodide - Acyl Chloride   
c) Platinum Complexes
d) Aluminum Chloride - Sodium Iodide - Acetonitrile
e) Zinc - Acyl Chloride
f) Trimethylsilyl Iodide    

IV) Selectivity in Dealkylation Of Ethers

a) Selective Dealkylation of Alkyl Ether   
b) Selective Dealkylation of Aryl Ether   
c) Selective Dealkylation of Allyl Ether   
a) Selective Dealkylation of Benzyl Ether   

V) Conclusion

VI) References