Friday, April 24, 2020

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




Asymmetric Addition of Alkylzinc Reagents to Cyclic α,β-Unsaturated Ketones and a Tandem Enantioselective Addition/Diastereoselective Epoxidation with Dioxygen




Applications of 1-Alkenyl-1,1-Heterobimetallics in the Stereoselective Synthesis of Cyclopropylboronate Esters, Trisubstituted Cyclopropanols and 2,3-Disubstituted Cyclobutanones




Applications of 1-Alkenyl-1,1-Heterobimetallics in the Stereoselective Synthesis of Cyclopropylboronate Esters, Trisubstituted Cyclopropanols and 2,3-Disubstituted Cyclobutanones




Visible-Light-Induced Aza-Pinacol Rearrangement: Ring Expansion of Alkylidenecyclopropanes




Arylation and Vinylation of Alkenes Based on Unusual Sequential Semipinacol Rearrangement/Grob Fragmentation of Allylic Alcohols

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BIOMOLECULES CHEMISTRY CLASS 12

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