Friday, October 18, 2019

organic chemistry - Stereoselective enolate formation with different bases: Does the addition of a base NR3 to a ketone affords the cis or the trans enolate?


I'm wondering if the addition of a base of type $\ce{NR_3}$ (R: alkyl) to a ketone (e.g. 3-pentanone or 4-heptanone) results in the cis or trans-enolate.


I'd like to ask here about four cases:




  1. $\ce{NMe_3}$ (small)

  2. $\ce{NMeEt_2}$ (medium)

  3. $\ce{NEt_3}$ (big)

  4. $\ce{N(iPr)_2Et}$ (very bulky)


Maybe smaller bases as 1 or 2 usually give the trans-enolate, and bulkier bases such as 3 or even 4 affords the cis-enolate. (That's what I read, but I'm not able to understand why.) Is there a good explanation that rationalizes which enolate is formed, the cis or the trans?


Sterically hindered bases forms the the kinetic enolate. For deprotonation of 3-Methyl-4-heptanone I assume the enolate at the linear unbranched chain site, that's clear for me, but kinetic/thermodynamic enolate has nothing to do with cis/trans enolate or does it?




Related: Does the addition of base to 3-pentanone give the cis or trans enolate?




No comments:

Post a Comment

digital communications - Understanding the Matched Filter

I have a question about matched filtering. Does the matched filter maximise the SNR at the moment of decision only? As far as I understand, ...