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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.


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.


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.