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Rearrangements

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, Synlett, 2011, 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., 2003, 125, 9544-9545.


Dual-Hydrogen-Bond Donor and Brønsted Acid Cocatalysis Enables Highly Enantioselective Protio-Semipinacol Rearrangement Reactions
M. A. S. Blackburn, C. C. Wagen, M. R. Bodrogean, P. M. Tadross, A. J. Bendelsmith, D. A. Kutateladze, E. N. Jacobsen, J. Am. Chem. Soc., 2023, 145, 15036-15042.


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. Ureņa, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2009, 131, 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. Ureņa, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2009, 131, 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., 2017, 19, 6288-6291.


Two Green Protocols for Halogenative Semipinacol Rearrangement
L. Song, Y. Zhou, H. Liang, H. Li, Y. Lai, H. Yao, R. Lin, R. Tong, J. Org. Chem., 2023, 88, 504-512.


Two Green Protocols for Halogenative Semipinacol Rearrangement
L. Song, Y. Zhou, H. Liang, H. Li, Y. Lai, H. Yao, R. Lin, R. Tong, J. Org. Chem., 2023, 88, 504-512.


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., 2008, 73, 7797-7799.