TY - JOUR
T1 - Taking advantage of lithium monohalocarbenoid intrinsic α-elimination in 2-MeTHF
T2 - controlled epoxide ring-openingen routeto halohydrins
AU - Ielo, Laura
AU - Miele, Margherita
AU - Pillari, Veronica
AU - Senatore, Raffaele
AU - Mirabile, Salvatore
AU - Gitto, Rosaria
AU - Holzer, Wolfgang
AU - Alcántara, Andrés R.
AU - Pace, Vittorio
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2021.
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/3/7
Y1 - 2021/3/7
N2 - The intrinsic degradative α-elimination of Li carbenoids somehow complicates their use in synthesis as C1-synthons. Nevertheless, we herein report how boosting such an α-elimination is a straightforward strategy for accomplishing controlled ring-opening of epoxides to furnish the corresponding β-halohydrins. Crucial for the development of the method is the use of the eco-friendly solvent 2-MeTHF, which forces the degradation of the incipient monohalolithium, due to the very limited stabilizing effect of this solvent on the chemical integrity of the carbenoid. With this approach, high yields of the targeted compounds are consistently obtained under very high regiocontrol and, despite the basic nature of the reagents, no racemization of enantiopure materials is observed.
AB - The intrinsic degradative α-elimination of Li carbenoids somehow complicates their use in synthesis as C1-synthons. Nevertheless, we herein report how boosting such an α-elimination is a straightforward strategy for accomplishing controlled ring-opening of epoxides to furnish the corresponding β-halohydrins. Crucial for the development of the method is the use of the eco-friendly solvent 2-MeTHF, which forces the degradation of the incipient monohalolithium, due to the very limited stabilizing effect of this solvent on the chemical integrity of the carbenoid. With this approach, high yields of the targeted compounds are consistently obtained under very high regiocontrol and, despite the basic nature of the reagents, no racemization of enantiopure materials is observed.
UR - http://www.scopus.com/inward/record.url?scp=85102388545&partnerID=8YFLogxK
U2 - 10.1039/d0ob02407d
DO - 10.1039/d0ob02407d
M3 - Article
C2 - 33599644
AN - SCOPUS:85102388545
SN - 1477-0520
VL - 19
SP - 2038
EP - 2043
JO - Organic and Biomolecular Chemistry
JF - Organic and Biomolecular Chemistry
IS - 9
ER -