Format:
Online-Ressource
ISSN:
1521-3765
Content:
Abstract: A highly efficient and straightforward aminoxylation of titanium (IV) enolates from (S)‐N‐acyl‐4‐benzyl‐5,5‐dimethyl‐1,3‐oxazolidin‐2‐ones with TEMPO has been developed. A wide array of functional groups on the acyl moiety, including alkyl and aryl substituents, olefins, esters, or α‐cyclopropyl, as well as α‐trifluoromethyl groups, are well tolerated. This transformation can therefore produce the α‐aminoxylated adducts in excellent yields with high diastereomeric ratios (d.r.). In turn, parallel additions to the α,β‐unsaturated N‐acyl counterparts give the corresponding γ‐adducts with complete regioselectivity in moderate to good yields. Removal of the piperidinyl moiety or the chiral auxiliary converts the resultant adducts into enantiomerically pure α‐hydroxy carboxyl derivatives, alcohols, or esters in high yields under mild conditions. Finally, a new mechanistic model based on the biradical character of the titanium (IV) enolates has been proposed.
In:
volume:20
In:
number:32
In:
year:2014
In:
pages:10153-10159
In:
extent:7
In:
Chemistry - a European journal, Weinheim : Wiley-VCH, 1995-, 20, Heft 32 (2014), 10153-10159 (gesamt 7), 1521-3765
Language:
English
DOI:
10.1002/chem.201402127
URN:
urn:nbn:de:101:1-2023011106590112096038
URL:
https://doi.org/10.1002/chem.201402127
URL:
https://nbn-resolving.org/urn:nbn:de:101:1-2023011106590112096038
URL:
https://d-nb.info/1277739005/34
URL:
https://doi.org/10.1002/chem.201402127
Bookmarklink