Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
Author: Subject: turbo hauser base effect on some compounds

Posts: 13
Registered: 13-12-2018
Member Is Offline

[*] posted on 27-2-2019 at 15:45
turbo hauser base effect on some compounds

i was reading about turbo-hauser bases
and that common ones are
iPr2NMgCl·LiCl, iPr-Turbo-Hauser base

TMPMgCl·LiCl, TMP-Turbo-Hauser base

i also read that those two differ in their reactions

[the 9th picture down (here)]

“iPr2NMgCl·LiCl can show a different reactivity compared to TMPMgCl·LiCl. Armstrong et al. showed that the TMP-Turbo-Hauser base easily metalates ethyl-3-chlorobenzoate in the C2 position, while the same reaction carried out with the iPr-Turbo-Hauser base resulted in no metalation at all. Instead, an addition-elimination reaction occurs.[5]”

[5] Armstrong D. R.; García–Álvarez, P.; Kennedy, A. R.; Mulvey, R. E.; Parkinson, J. A. (2010). "Diisopropylamide and TMP Turbo-Grignard Reagents: A Structural Rationale for their Contrasting Reactivities". Angew. Chem. Int. Ed. 49 (18): 3185–3188. doi:10.1002/anie.201000539. PMID 20352641.

i noticed that it addition-substitution reacted with an ethyl ester, so i was wondering if it would replace
1) OH acid
2) H aldehyde
3) OMe methyl ester
i assume it would work better with the OH, (but what about the aldehyde?)

i was then wondering if it was only directed because of the 2-Chloro,

but anyway, the two substitutions that i am wondering about are regarding
the idea of Et2NMgCl•LiCl substituting the OH in the attached molecule and also in the case of m-Toluic acid (producing DEET in that case).

i was wondering if it would preferentially metallate the molecules where there are pi orbitals at the double bonds.

474A804B-0FDC-4183-B381-E2A5B383F23D.jpeg - 485kB 9AFBF2EB-DCFB-48AD-A003-ED90F9FAE595.png - 850kB 2F704CE3-6DF5-468C-8B35-78FE9E34E32F.png - 913kB 630106DF-D8A0-4EE9-8513-BC7F6812D51E.png - 809kB DF9D45C6-26CE-4683-9EA5-58771AAF1AD0.png - 521kB 864EA7F4-ACD1-43DE-9959-CDB586CF96A8.png - 714kB 37961F8D-8F9C-4E67-BB1A-EE6893B9FBDC.png - 825kB 66514140-5471-4AE7-8346-EDF60B2C19F3.png - 740kB AB503EF5-6A22-4C88-885B-B6E560013483.png - 670kB 305E121F-54F9-493D-89B7-B2BD3E87F033.png - 929kB 2A81BF01-E6C4-4FE9-BC3C-8FE848F05BFE.png - 555kB

[Edited on 28-2-2019 by pomegranate]

[Edited on 28-2-2019 by pomegranate]
View user's profile View All Posts By User

  Go To Top