Pinacol Rearrangement

Pinacol Rearrangement

In The Conversion That Gave Its Name To This Reaction, The Acid-catalyzed Elimination Of Water From Pinacol Gives t-butyl Methyl Ketone.


Mechanism Of The Pinacol Rearrangement

This Reaction Occurs With A Variety Of Fully Substituted 1,2-diols, And Can Be Understood To Involve The Formation Of A Carbenium Ion Intermediate That Subsequently Undergoes A Rearrangement. The First Generated Intermediate, An α-hydroxycarbenium Ion, Rearranges Through A 1,2-alkyl Shift To Produce The Carbonyl Compound. If Two Of The Substituents Form A Ring, The Pinacol Rearrangement Can Constitute A Ring-expansion Or Ring-contraction Reaction.

Recent Literature


Polymer-Mediated Pinacol Rearrangements
C. Pavlik, M. D. Morton, M. B. Smith, Synlett2011, 2191-2194.


Asymmetric Addition Of Alkylzinc Reagents To Cyclic α,β-Unsaturated Ketones And A Tandem Enantioselective Addition/Diastereoselective Epoxidation With Dioxygen
S.-J. Jeon, P. J. Walsh, J. Am. Chem. Soc.2003125, 9544-9545.


Applications Of 1-Alkenyl-1,1-Heterobimetallics In The Stereoselective Synthesis Of Cyclopropylboronate Esters, Trisubstituted Cyclopropanols And 2,3-Disubstituted Cyclobutanones
M. M. Hussain, H. Li, N. Hussain, M. Ureña, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc.2009131, 6516-6524.


Applications Of 1-Alkenyl-1,1-Heterobimetallics In The Stereoselective Synthesis Of Cyclopropylboronate Esters, Trisubstituted Cyclopropanols And 2,3-Disubstituted Cyclobutanones
M. M. Hussain, H. Li, N. Hussain, M. Ureña, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc.2009131, 6516-6524.


Visible-Light-Induced Aza-Pinacol Rearrangement: Ring Expansion Of Alkylidenecyclopropanes
W.-D. Liu, G.-Q. Xu, X.-Q. Hu, P.-F. Xu, Org. Lett.201719, 6288-6291.


Arylation And Vinylation Of Alkenes Based On Unusual Sequential Semipinacol Rearrangement/Grob Fragmentation Of Allylic Alcohols
D.-Y. Yuan, Y.-Q. Tu, C.-A. Fan, J. Org. Chem.200873, 7797-7799.