Lesson 1
Acyl Insertion of O, NH, and CH2 1
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Prof. McBride, J. Michael, CHEM 125b, Freshman Organic Chemistry II, Spring 2011, YALE Open Courses: Yale University, Chemistry (Accessed 20/09/2014), http://oyc.yale.edu/chemistry/chem-125b/lecture-35 License: Creative Commons BY-NC-SA When a nucleophilic atom bearing a good leaving group attacks a carbonyl group, an adjacent Rgroup can migrate to the new atom, inserting it into the R-acyl bond. This mechanism can insert O, NH, or CH2 groups into the acyl bond with informative stereospecificity in the case of the Beckmann rearrangement of oximes. Acid dissociation of protons a to a carbonyl group to form enolates, and the ease of forming enols, gives α-carbons nucleophilic reactivity under both basic and acidic conditions. This explains H/D exchange and racemization as well as halogenation and alkylation of α-carbons.

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