Lecture 35 - Acyl Insertions and α-Reactivity

author: J. Michael McBride, Department of Chemistry, Yale University
recorded by: Yale University
published: Aug. 19, 2014,   recorded: June 2011,   views: 1395
released under terms of: Creative Commons Attribution No Derivatives (CC-BY-ND)
Categories

See Also:

Download Video - generic video source Download yalespan125bs2011_mcbride_lec35_01.mp4 (Video - generic video source 563.9 MB)

Download Video Download yalespan125bs2011_mcbride_lec35_01_640x360_h264.mp4 (Video 146.1 MB)

Download subtitles Download subtitles: TT/XML, RT, SRT


Help icon Streaming Video Help

Related Open Educational Resources

Related content

Report a problem or upload files

If you have found a problem with this lecture or would like to send us extra material, articles, exercises, etc., please use our ticket system to describe your request and upload the data.
Enter your e-mail into the 'Cc' field, and we will keep you updated with your request's status.
Lecture popularity: You need to login to cast your vote.
  Bibliography

Description

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. Although the migrating groups are formally anionic, relative migratory aptitudes show that they give up electron density during rearrangement. 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.

Link this page

Would you like to put a link to this lecture on your homepage?
Go ahead! Copy the HTML snippet !

Write your own review or comment:

make sure you have javascript enabled or clear this field: