| Attributs | Valeurs |
|---|
| type
| |
| Is Part Of
| |
| Subject
| |
| Title
| - Addition of Hetero Allenyl Copper Reagents to Aldehydes:Scope and Behavior
|
| has manifestation of work
| |
| related by
| |
| Author
| |
| Abstract
| - Cyanocuprates derived from propargylic amines or ethers react with aldehydes to give regioselectivelythe corresponding anti-homopropargylic alcohols with a high level of diastereoselectivity. Such selectivitycould be obtained independently of the nature of the heteroatom (amine or ethers) or the acetylenicsubstituents. Excellent selectivities can be reached regardless of the aldehydes used, remarkably alsowith vinylic or acetylenic ones. A reactivity scale for the cuprates bearing different acetylenic substituentswas established to be: SiMe3>Ph> Et. The rate of the addition reaction to aldehydes was also foundto be slowed down in the presence of HMPA underlining the crucial role of the Li counterion. DFTcalculations have shown that the relationship between the rate and the acetylenic substituent is notconnected to a possible metallotropic equilibrium but to the stability of the reactive allenic species comparedto the less-stable propargylic isomer.
|
| article type
| |
| is part of this journal
| |
